Discovery of platinum (II) and azulene derivative cocrystals with fluorinated cyanoaromatics

Pentacyano-trifluoromethyl benzene was synthesized using a novel technique. Before isolation, it was noted that plate like crystals had formed leading to study regarding the ability of acetic acid to co-crystallize with pentacyanotrifluoromethyl benzene. The crystal structure of acetic acid with pentacyanotrifluoromethyl benzene was obtained and analyzed. This analysis most demonstrates that there is an anionic hole in the center of the pentacyano-trifluoromethyl benzene ring, which is particularly important, as it demonstrates that pentacyano-trifluoromethyl benzene has the potential to form a new class of charge-transfer complexes. Azulene derivatives are a severely underexplored subset of organic heterocyclic aromatic compounds with unique properties. Though p stacking of many polycyclic aromatic compounds and cyanoaromatics have been reported, this research has not been completed regarding azulene and azulene derivatives. Crystal structures of 4,6,8- trimethylazulene with pentacyano-trifluoromethyl benzene and tetrafluoroterephthalonitrile, were obtained and analyzed. A crystal structure of guaiazulene with pentacyano-trifluoromethyl benzene were obtained and analyzed. While platinum compounds have been identified as being useful in healthcare, the synthesis of ligands and analysis of their chemical properties has slowed. Though p stacking of transition metal complexes with fluorinated aromatic cyanocarbons has been studied, this field is still largely underexplored. A crystal structures for Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and tetrafluoroterephthalonitrile was obtained and analyzed.

DISCOVERY OF PLATINUM (II) AND AZULENE DERIVATIVE COCRYSTALS WITH FLUORINATED CYANOAROMATICS by Anneke Enquist A Senior Honors Thesis Submitted to the Faculty of The University of Utah In Partial Fulfillment of the Requirements for the Honors Degree in Bachelor of Science In Biochemistry Approved: __________ Thomas Richmond Thesis Faculty Supervisor _____________________________ Matthew S. Sigman Chair, Department of Chemistry __________ _____________________________ Monisha Pasupathi, PhD Dean, Honors College Thomas Richmond Honors Faculty Advisor May 2024 Copyright © 2024 All Rights Reserved ABSTRACT Pentacyano-trifluoromethyl benzene was synthesized using a novel technique. Before isolation, it was noted that plate like crystals had formed leading to study regarding the ability of acetic acid to co-crystallize with pentacyanotrifluoromethyl benzene. The crystal structure of acetic acid with pentacyanotrifluoromethyl benzene was obtained and analyzed. This analysis most demonstrates that there is an anionic hole in the center of the pentacyano-trifluoromethyl benzene ring, which is particularly important, as it demonstrates that pentacyano-trifluoromethyl benzene has the potential to form a new class of charge-transfer complexes. Azulene derivatives are a severely underexplored subset of organic heterocyclic aromatic compounds with unique properties. Though p stacking of many polycyclic aromatic compounds and cyanoaromatics have been reported, this research has not been completed regarding azulene and azulene derivatives. Crystal structures of 4,6,8trimethylazulene with pentacyano-trifluoromethyl benzene and tetrafluoroterephthalonitrile, were obtained and analyzed. A crystal structure of guaiazulene with pentacyano-trifluoromethyl benzene were obtained and analyzed. While platinum compounds have been identified as being useful in healthcare, the synthesis of ligands and analysis of their chemical properties has slowed. Though p stacking of transition metal complexes with fluorinated aromatic cyanocarbons has been studied, this field is still largely underexplored. A crystal structures for Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and tetrafluoroterephthalonitrile was obtained and analyzed. ii TABLE OF CONTENTS ABSTRACT ii INTRODUCTION 1 METHODS PROCEDURE 1: Synthesis of C! (CN)" CF# 6 PROCEDURE 2: Synthesis of 4,6,8-Trimethylazulene 7 PROCEDURE 1: Synthesis of Platinum (II) Complexes 10 CO-CRYSTALLIZATION METHODS 11 COMPOUND SPECIFIC METHODS 14 COLLECTION OF UV-VIS DATA 17 INSTRUMENTATION 18 RESULTS AND DISCUSSION ACETIC ACID WITH C! (CN)" CF# 36 4,6,8-TRIMETHYLAZULENE WITH FLUORINATED … 22 GUAIAZULENE WITH C! (CN)" CF# 28 PLATINUM COCRYSTALS 32 ACETIC ACID WITH C! (CN)" CF# 36 GENERAL RESULTS 19 CONCLUSION AND FUTURE DIRECTIONS 40 REFERENCES 42 APPENDIX A 46 iii 1 INTRODUCTION This thesis explores and further characterizes pentacyano-trifluoromethyl benzene (C! (CN)" CF# ), a novel compound that was recently synthesized in the Richmond Group.1 This thesis will present a new method of synthesis and isolation of this complex. This novel methodology interestingly yielded cocrystals of C! (CN)" CF# and acetic acid, which serves to conclude that there is an anionic hole present in the ring of this molecule, which makes it an ideal candidate for the creation of a new class of charge-transfer complexes. Charge transfer complexes consist of an electron-rich donor substrate and an electron poor acceptor substrate. When parent compounds combine, creating a chargetransfer complex, new properties often emerge. These complexes can have ambipolar, semiconducting, metallic, and even superconducting properties,2 and characteristically are brightly colored. C! (CN)" CF# demonstrates face-to-edge stacking when crystallized alone,1 but face-to-face stacking when cocrystallized. This face-to-face stacking allows for a high degree of pi-pi orbital interactions, which increases the exchange of the charge between compounds.3 Substituting aromatic rings provides an opportunity to alter the electronic properties of these aromatic rings, allowing us to create cationic or, in the case of C! (CN)" CF# , anionic holes at the center of the aromatic ring. In addition, this thesis will explore and characterize cocrystals formed from a variety of platinum (II) ligands, azulene derivatives, and cyanoaromatic compounds, using infrared spectroscopy (IR) for characterization of compounds, ultraviolet-visible 2 Spectroscopy (UV-Vis) for evidence of solute interaction in solution, and x-ray crystallography for structure determination. Cocrystals are a particularly useful yet seriously underexplored component of chemistry. Cocrystals date back to 1844, with the co-crystallization of quinone (yellow) and hydroquinone (colorless) by Friedrich Wöhler yielding quinhydrone (green).4 Despite a visible change, the structure and makeup of quinhydrone wasn’t determined until 1958. Though the first application of crystal engineering was applied by Schmidt using cinnamanic acid derivatives in 1964, the field of crystallization and its many applications didn’t explode until the 1980s.5 Many compounds have been crystallized and studied, but very few cocrystallized compounds exist. As of 2009, less than 0.5% of the crystals in the Cambridge Structural Database were classified as cocrystals.6 While that percentage has increased, cocrystals still make up a minute portion of the database. Though the structure and composition of any molecule defines many of its properties, the three-dimensional orientation, organization, and interactions of molecules in a crystalline lattice at the very least influence and might determine multiple properties of the substance.7 Cocrystal engineering has applications in energetic materials production, textiles production, agrochemistry, chemical separation, and the pharmaceutical industry, where the term pharmaceutical cocrystals – a solid cocrystal former component with a molecular or ionic API – has gained traction.7 The pharmaceutical applications of cocrystals are particularly promising given that a recent estimate placed 2/3 of potentially useful drug candidates as insoluble in water.8 Through co-crystallizing these insoluble drug candidates with small molecules soluble in water, we can potentially increase the amount of drug candidates for treatment of a variety of diseases. 3 While cocrystals show promise in the realm of pharmaceuticals, platinum complexes have proven uses, with agents such as cisplatin, oxaliplatin, and carboplatin being used in the chemotherapeutic eradication of cancer. Despite the usefulness of platinum complexes, discovery and characterization of novel platinum ligands has slowed. Most of the current research regarding platinum (II) complexes revolves around the production of cyclometalated platinum complexes and its phosphorescent properties, primarily the production and improvement of organic light-emitting diodes (OLEDs).9 Previous work done by the Richmond group focused on exploring the properties of cocrystals of charged benzene derivatives and polycyclic aromatic compounds. Previously, cyanoaromatics have demonstrated the greatest impact on increasing the strength of the charge transfer interactions of a parent benzene compound, whilst still affording the overall molecule stability. More recent work has focused on characterizing and exploring the stacking characteristics of cyanoaromatic compounds. Figure 1: A depiction of the electrostatic potential of tetrafluoroterephthalonitrile, using B98-V/cc-pVDZ calculation methods, showing ChEIPG partial atomic charges, completed by Dr. Ryan Steele at the University of Utah.7 4 Figure 2: A depiction of the electrostatic potential of pentacyano-trifluoromethyl benzene, using B98-V/cc-pVDZ calculation methods, showing ChEIPG partial atomic charges, completed by Dr. Ryan Steele at the University of Utah.7 The inverted electrostatic nature of these cyanoaromatic compounds (Figures 1 and 2), allows the cyanoaromatic compounds to interact with potential electron donors such as the 𝑑$ % orbital of platinum (II). Recent work done by Kevin Lutz, a former graduate of the Richmond group, confirms this interaction.10 In continuing this research, additional platinum (II) complexes were synthesized and co-crystallized with fluorinated cyanocarbons. Figure 3: Visual Depiction of Charges on Azulene 5 Figure 4: Plot of the Electrostatic Potential for Azulene on the Isodensity Surface Defined by a value of 0.005 𝑎&'# . The color coded potential (when interacting with a positive unit charge) ranges from -13 (red) to 13 (blue) kcal/mol. The zero of the electrostatic potential is given by the green/blue border.11 Another compound of particular interest is azulene and azulene derivatives. Azulene is an aromatic isomer of naphthalene that consists of a positively charged seven membered ring and a negatively charged five membered rings (Figure 3). Very few azulene derivatives have been synthesized, isolated, and characterized, despite azulenes noted anti-inflammatory, antimicrobial, and antiallergic applications.12 Though there has been a recent uptick in research regarding the properties of azulene and its derivatives, the field is still grossly underexplored. As mentioned previously, the Richmond group has historically focused on exploring the properties of cocrystals of cyanoaromatics and polycyclic aromatic compounds. Recently, the group has generated and analyzed cocrystals using naphthalene (azulene’s isomer) and naphthalene derivatives with the intent to eventually compare the co-crystalline properties of naphthalene and azulene. 6 These cocrystal will be analyzed using a variety of techniques. Of these, X-ray Crystallography is the gold standard. Historically, X-ray crystallography has been used to determine structure of single crystals, cocrystals, and protein and nucleic acid structures – most famously, DNA. A review of X-ray crystallography concludes that “Crystallographic studies play is vital role in many disciplines including materials science, pharmacology, and molecular biology. [It] is the most comprehensive technique available to determine molecular structure.”13 While this technique is particularly useful, it depends on the scientist effectively isolating a relatively pure cocrystal that has edges and reflects and refracts light. These techniques are later explored in the methods section. NMR is not particularly useful in characterizing cocrystals, but it is useful in identifying and characterizing a variety of homogenous starting materials, and gauging purity of hydrogenated or fluorinated starting materials. Purer starting components make it easier to isolate relatively pure cocrystals, as there are fewer potential contaminants. Various spectroscopic methods can also be utilized in characterizing cocrystalline compounds. Just as quinhydrone possessed a unique color from its substituents, compounds that present a color change when mixed in solution can be analyzed using Ultraviolet-Visible spectrum. This data further characterizes a cocrystal. Historically, this data has led to breakthroughs in understanding potential molecular switches and lowering the excitation energies.14 Infrared Spectroscopy also characterizes co-crystalline compounds, and can be used to compare starting materials to the cocrystal, where various signals are combined or amplified. The components of each starting material in the cocrystal are not transposable to the IR of each respective starting material, as demonstrated by daidzein cocrystals.15 7 METHODS Procedure I: Synthesis of C! (CN)" CF# Figure 5: The Formation of Pentacyano-trifluoromethyl benzene (C! (CN)" CF# ) The synthesis of C! (CN)" CF# was completed using the methods outlined by Beck and co-workers in a 1992 patent.16 24.5 grams of sodium cyanide is added to a solution of 24.3 grams a,a,a,2,3,5,6-heptafluoro-p-tolunitrile in 250 mL of dry acetonitrile in a stoppered round bottom flask with a magnetic stir bar. The mixture should be colored yellow orange at this point. The mixture is stirred stoppered for 10 days, at which point it is colored a deep red. At this point, the mixture is filtered, and the filtrate is washed with acetonitrile and concentrated in a rotary evaporator with a bath temperature of 30 °C. To remove any heptafluoro- compound, the concentrated filtrate is stirred with 250 mL of dry dichloromethane at room temperature, filtered, and washed with dichloromethane to yield 31.0 grams of the red sodium salt. Using 1.00 gram of the above sodium salt is dissolved into 5 grams of glacial acetic acid. The solution is allowed to stand at room temperature for three days 50 mL of water is added, and the precipitate is filtered, and washed with water. Yield of 0.68 grams. While the compound would ideally be white, the isolated compound was a more cream with a very slight reddish tint. 8 Procedure II: Synthesis of 4,6,8-Trimethylazulene Figure 6: Reaction yielding 4,6,8-Trimethylazulene12 The synthesis of 4,6,8-Trimethylazulene was completed by Dr. David Baumann based on a 1983 synthetic route.17 To synthesize the 4,6,8-Trimethylazulene, a 25 mL round bottomed flask is fitted with a distillation column, distillation head, condenser, and adaptor for fractional distillation. A 25-mL graduated cylinder is used as a receiver and placed in an ice bath. 15 mL of dicyclopentadiene is placed in the distillation flask and distilled with the temperature below 80 °C to crack the cyclopentadiene dimer. More than 10 mL should be collected. The cyclopentadiene must be used shortly after distillation. In a dry 125 mL Erlenmeyer flask fitted with a rubber stopper place 8.0 g of sodium methoxide. 50 mL of dry dimethylformamide keeping the Erlenmeyer flask stoppered. The flask is cooled in an ice bath and 10 mL of cyclopentadiene is quickly added to the flask. The flask is then swirled, keeping it cool. The suspension will be brown. After 1-2 minutes the solid pyrylium salt (about 4 grams) is added and the flask is again stoppered, and a deep azure color should develop. If no blue color is observed, no azulene can be isolated. The flask is then allowed to stand at room temperature for one hour and is occasionally swirled. The suspension is then diluted with 60 mL of water and the aqueous layer is washed with 20 mL of petroleum ether three times. The layers should 9 be dark and difficult to see during the first extractions, but these layers can be made more distinct by shining a bright light behind the layers to better visualize the distinction. Repeat this process 3-4 times. The maroon petroleum ether solution is then dried over anhydrous magnesium sulfate and filtered before the solvent is evaporated on a steam bath yielding 1-2 grams of a dark oily residue. A chromatography column is the packed by placing a glass wool plug above the stopcock. A 1 cm layer of sand is added atop the glass wool, and the column is filled with petroleum ether and 15 grams of alumina. Add a 1 cm layer of sand to the top of the alumina. The distillation residue is then diluted with 0.5 mL of petroleum ether and pipetted tot eh top of the column. Continue using petroleum ether as the eluent. A purpleviolet band should appear on the column, and it is this band that is then collected as a separate fraction. The solution is then evaporated to leave 0.5-2.0 grams of an oily solid. The azulene is then recrystallized from ethanol to give small crystals in the shape of needles. The final product was gifted by Dr. David Baumann. Procedure III: Synthesis of Platinum (II) Complexes Figure 7: Creation of PtCl2(SMe2)2 Figure 8: Synthesis of PtMe2(SMe2)2 dimer 10 The two-step synthesis of the (Pt)ACAC complexes was adapted from work done by Hudson, Blight and Wang.18 The first step is the synthesis of a PtMe2 (SMe)2 dimer which is done by adding 25 mL of water to a 100 mL Erlenmeyer Flask, and adding dimethyl sulfide dropwise (1.9 grams, 30 mmol), solid potassium tetrachloroplatinate (2 grams, 4.83 mmol), and a stir bar to form a pink precipitate. Cis/trans-[PtCl% (SMe% )% ]% is then isolated by heating the solution to 100 °C for 30 minutes. After this time has elapsed, the flask is removed from heat and the mixture is allowed to cool to room temperature. The solution is then extracted using dichloromethane three times in increments of 20 mL in a separatory funnel. The extract is then dried using anhydrous magnesium sulfate, which is removed prior to concentrating the extract under rotary evaporation to yield a vivid yellow solid. Figure 9: Reaction for One-Pot Synthesis of Benzoquinoline (Pt)2,2,6,6-tetramethyl3,5-heptanedione Figure 10: Reaction for One-Pot Synthesis of Benzoquinoline (Pt)Acetylacetone 11 The second step is the addition of the cyclometalating complex and ACAC complex to the isolated platinum dimer which is done at ambient temperature under open air in a 20 mL screw cap scintillation vial. To the vial, one equivalent of 7,8benzoquinoline was added to the platinum dimer (100 milligrams, 0.17 mmol), three milliliters of THF, and a magnetic stir bar. This reaction is stirred for one hour. After that point, a solution of trifluoroacetic acid is added to the mixture (1 mL, 0.35 M in THF) and is stirred in for another 30 minutes. A solution of Na(b-diketone) (where the diketone is either acetylacetone or 2,2,6,6-tetramethyl-3,5-heptanedione) is then prepared by reacting 0.70 mmol of diketone with 0.70 mmol of finely crushed NaOH in 2 mL of methanol. The diketone solution is then added dropwise to platinum dimer solution and allowed to stir for three days. The solution is then partitioned between water and dichloromethane. The organic layer is washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue is purified on a silica plug using dichloromethane as an eluent to give an analytically pure metal. Co-Crystallization Methods The platinum and azulene complexes above were co-crystallized with both C! (CN)" CF# and C! (CN)% F( (tetrafluoroterephthalonitrile) using one of three techniques: two-chamber vapor diffusion, liquid diffusion, or evaporation. Co-crystals of the azulene derivatives and cyanocarbons were often set up in a vapor diffusion chamber for 48 hours, and then allowed to evaporate. Co-crystals of the platinum complexes and pentacyano-trifluoromethyl benzene were done in a liquid-liquid diffusion as the two 12 precipitated when added to a solvent together. Co-crystals of the platinum complexes and C! (CN)% F( were obtained via vapor diffusion and evaporation methods as liquid-liquid diffusion did not yield co-crystals, but individual compound crystals. Figure 11: Diagram of Two-Chamber Vapor Diffusion10 Two-chamber vapor diffusion (Figure 11) was used most frequently, as it was the easiest and worked for the overwhelming majority of compounds. Two chamber vapor diffusion began by weighing out a 1:1 molar ratio of the compounds and dissolving them in an organic solvent (toluene and methanol, dichloromethane, or dichloroethane). Then, the solution is filtered through a frit into a smaller scintillation vial with the screw cap off to rid the solution of potential impurities. The smaller, capless scintillation vial is then placed into a 20 mL scintillation vial and volatile solvent (pentane) is added. The lid to the 20 mL scintillation vial is closed and the setup is left undisturbed for a minimum of 24 hours. Ideally, this process would form crystals, as the co-crystals should be insoluble in the more volatile substance. However, some samples crystallized in this fashion required a second step: evaporation. After the vapor diffusion had been allowed to sit for a minimum of 24 hours, the top of the 20 mL scintillation vial was removed, and the solution was allowed to evaporate leaving behind crystals. Evaporation is a simple deposition on the glass surface of the vial of precipitate, trapping in impurities, leaving a 13 contaminated crystal. Evaporation also tends to leave less crystals behind than the other methods. Figure 12: Diagram of Liquid-Liquid Diffusion10 Liquid-liquid diffusion (Figure 12) was used to crystallize compounds that precipitate when placed into solution. This method begins the same way a two-chamber vapor diffusion, by weighing out a 1:1 molar ratio of each of the compounds. For this experiment, the platinum compounds were dissolved in dichloroethane and the cyanocarbon was dissolved in toluene. The two solutions were filtered separately, and then carefully layered in an NMR tube. The tube is then capped and left undisturbed for a minimum of 48 hours. As this method of diffusion is significantly slower than a twochamber vapor diffusion, it prevents the pentacyano-trifluoromethyl benzene from precipitating with the platinum compound. Not all crystals discussed in this work were isolated using two-chamber vapor diffusion or liquid-liquid diffusion. While synthesizing C! (CN)" CF# in glacial acetic acid, it was noted that large plate-like crystalline structures had formed. In the spirit of 14 scientific curiosity, these crystals were dried over a vacuum for over an hour, and then washed with a small amount of diethyl ether. After it was noted that even small amounts of diethyl ether were degrading the crystals, crystals were analyzed using infrared spectroscopy and x-ray crystallography. The general procedure for using the diffractometer was the same for each crystal. First, the crystals were extracted from the crystallization vessel using an organic oil, which they are then suspended in on a microscope slide. A suitable crystal to analyze in identified. The crystal is then picked up on a micro-meter sized loop and mounted onto the diffractometer. The diffractometer has a continuous stream of vaporized nitrogen cooling down both the crystal and the oil. When cooled, the oil hardens the crystals in place. The crystal is then manually centered, and Cu Ka radiation is used for the measurements, which are taken every 0.5° at an exposure of 0.1 seconds. The diffraction patter is collected and sent to the computer, which analyzes it, and solves the crystal structure, yielding the data in Appendix A. All x-ray diffraction and crystal structure determination were completed by Ryan Vanderlinden. Compound Specific Methods C! (CN)" CF# with Glacial Acetic Acid: When synthesizing C! (CN)" CF# , after stirring the solution in glacial acetic acid, large plate-like crystals were evident. Instead of washing these plates with water to remove the excess acetic acid, these crystals were dried over a vacuum for over an hour and washed with ether to remove any excess solvent. Washing with ether degraded the crystals, but still permitted smaller crystalline structures to be prevalent. Crystal structure was obtained and analyzed. 15 Figure 13: Cocrystal of Acetic Acid and C! (CN)" CF# (x-axis = 6 mm) 4,6,8-Trimethylazulene (5.4 mg) and C! (CN)" CF# (8.2 mg) were added as 1:1 molar equivalent to 5 mL toluene and dissolved. The C! (CN)" CF# was not dissolving, so approximately 1 mL of methanol was added, dissolving the C! (CN)" CF# . The mixture was filtered through a frit and a vapor diffusion chamber was set up with pentane being allowed to diffuse in. Crystals were obtained and analyzed. Figure 14: Cocrystal of 4,6,8-Trimethylazulene and C! (CN)" CF# (x-axis = 6 mm) 4,6,8-Trimethylazulene (5.2 mg) and C! (CN)% F( (4.6 mg) were added as 1:1 molar equivalent to 5 mL of toluene and 1 mL of methanol and dissolved. The mixture was filtered through a frit and a vapor diffusion chamber was set up with pentane being allowed to diffuse in. After 48 hours, the mixture was dumped into a 20 mL scintillation 16 vial and allowed to evaporate completely. Unfortunately, after the crystal structure was obtained using the X-ray diffractometer, the crystals were lost in transport prior to an IR being obtained. Figure 15: Cocrystal of 4,6,8-Trimethylzaulene and C! (CN)% F( Guaiazulene (17.1 mg) and C! (CN)" CF# (20.3 mg) were dissolved in ~5 mL of toluene and methanol. The mixture was filtered through a frit and a vapor diffusion chamber was set up. Pentane was allowed to diffuse in for 24 hours. The solution was then allowed to evaporate. Crystals were obtained and analyzed. Figure 16: Cocrystal of Guaiazulene and C! (CN)" CF# 17 Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and C! (CN)% F( .were added as 1:1 molar equivalent separately, each to an aliquot of a 1.5 mL solution of 1 mL dichloromethane and 0.5 mL of methanol. Each individual solution was filtered through a frit and each solution was layered carefully in an NMR tube to allow liquid-liquid diffusion. Crystals were obtained and analyzed. Figure 17: Cocrystal of Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and C! (CN)% F( . (x-axis = 6 mm) Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and C! (CN)" CF# were added as 1:1 molar equivalent separately, each to an aliquot of a 1.5 mL solution of 1 mL dichloromethane and 0.5 mL of methanol. Each individual solution was filtered through a frit and each solution was layered carefully in an NMR tube to allow liquid-liquid diffusion. Crystal structure could not be obtained, but an IR was taken. Figure 18: Cocrystal of Benzoquinoline(Pt)Acetylacetone and C! (CN)" CF# (x-axis=6mm) 18 The following crystallizations yielded no viable crystals: 4,6,8-trimethylazulene and benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione, benzoquinoline(Pt)2,2,6,6tetramethyl-3,5-heptanedione and C! (CN)% F( , guaiazulene and C! (CN)% F( , benzoquinoline(Pt)acetylacetone and C! (CN)" CF# , and benzoquinoline(Pt)acetylacetone and C! (CN)% F( . Collection of UV-Vis Data Two solutions of 0.5 mg/mL of guaiazulene were made by weighing out 60 mg and dissolving in 120 mL of either dichloromethane or a solution of toluene and methanol (90% toluene, 10% methanol). Five of the aliquots of the 0.5 mg/mL of guaiazulene in dichloromethane had C! (CN)% F( added to them to create C! (CN)% F( concentrations of 0.25 mg/mL, 0.5 mg/mL, 0.75 mg/mL, 1.0 mg/mL, and 1.25 mg/mL. Five of the aliquots of the 0.5 mg/mL of guaiazulene in toluene and methanol had C! (CN)" CF# added to them to create C! (CN)" CF# concentrations of 0.25 mg/mL, 0.5 mg/mL, 0.75 mg/mL, 1.0 mg/mL, and 1.25 mg/mL. A solution of 0.5 mg/mL C! (CN)" CF# in toluene and methanol, and a solution of 0.5 mg/mL C! (CN)% F( in dichloromethane were also made. The instrument was calibrated between each experiment. A solution of an unknown, but constant concentration of 4,6,8-trimethylazulene (an accurate weight could not be obtained) was made by dissolving the azulene into 5.2 mL of 5 mL toluene and 0.2 mL of methanol. 4,6,8-Trimethylazulene was maintained at a 19 constant concentration and data from concentrations of C! (CN)" CF# at 0.5 mg/mL, 1.0 mg/mL, 2.0 mg/mL, 4.0 mg/mL, and 8.0 mg/mL. Instrumentation NMR experiments were performed on a Bruker AVANCE Neo 300. IR experiments were performed with a Nicolet ATR is50 infrared spectrophotometer. UV-Vis Experiments were performed with a Vernier GoDirect SpectroVisPlus in 1 cm glass cells controlled by an iPad. Crystal Structure was obtained and analyzed using a XtaLAB Syntergy R, DW system, HyPix diffractometer, which solved the structures using ShelXT 2019/2 with Olex2 as a graphical interface. Crystal structures were solved by Dr. Ryan Vanderlinden. The crystal data for each solved crystal is in Appendix A. 21 Figure 21: Ordered View of Acetic Acid and C! (CN)" CF# While these crystals were created accidentally, they provide a crucial insight into future research prospects. These crystals were large, and plate like in nature, which is interesting given their stacking. The C! (CN)" CF# stacks in a chevron pattern, which is flanked by hydrogen bonded acetic acid molecules which also follow a chevron like pattern with one another. The C! (CN)" CF# centroid coordinates with the edges of the acetic acid molecules, and the two molecules stack perpendicularly (face-to-edge) with one another. Because acetic acid coordinates with the centroid of C! (CN)" CF# , this crystal clearly demonstrates that there is an anionic hole in C! (CN)" CF# . It is also of note that this crystal structure is ordered, something that has not historically been capable with this compound in acidic solution. 22 Figure 22: IR Comparison of Acetic Acid and C! (CN)" CF# as Singular and Co-Crystals When comparing the IR of acetic acid and C! (CN)" CF# to their cocrystal, it is first noticed that the O-H stretch at 3000 cm-1 almost completely disappears from the cocrystal IR. In addition, there isn’t necessarily a significant shift or amplification of the 24 4,6,8-Trimethylazulene and C! (CN)" CF# demonstrate parallel (or face-to-face) stacking characteristics. Interestingly, despite being added as a 1:1 stochiometric ratio, the crystal itself displays a 2:1 stochiometric ratio, with twice the number of azulene derivatives as C! (CN)" CF# . Due to the anionic hole present in C! (CN)" CF# , it would be natural to assume that the centroid in C! (CN)" CF# , representing the center of that anionic hole, would connect most closely to the electron rich five-membered ring in each 4,6,8trimethylazulene molecules. Instead, each of the 4,6,8-trimethylazulene molecules display unique coordination with the C! (CN)" CF# , with the five-membered ring in the top 4,6,8-trimethylazulene coordinating most closely, and the seven-membered ring in the bottom 4,6,8-trimethylazulene coordinating most closely. Note that although the closest centroid distances flip, the closest points on both 4,6,8-trimethylazulene molecules to the C! (CN)" CF# centroid is consistently the carboncarbon bond between each ring. This patterning was also displayed in previous work completed by the Richmond Lab,7 and implies that the coordination of C! (CN)" CF# and 4,6,8-trimethylazulene is not primarily dependent on electronics. Finally, it should be noted that the trifluoromethyl group in C! (CN)" CF# does not seem to prefer a singular configuration but seems to prefer to crystallize in three configurations. This preference might be afforded to potential steric interactions of other configurations; however, without multiple experiments, the configuration preference of the trifluoromethyl group cannot be conclusively determined. 25 Figure 25: Expanded Unit of 4,6,8-Trimethylazulene and C! (CN)" CF# Though the expanded unit of 4,6,8-trimethylazulene and C! (CN)" CF# does not necessarily provide more information that the single unit does, it does confirm the 2:1 stochiometric ratio, and that the trifluoromethyl group exists in multiple configurations. Figure 26: 4,6,8-Trimethylazulene and C! (CN)% F( , Centroid Distances Figure 27: 4,6,8-Trimethylazulene and C! (CN)% F( , Centroid to Bond Distances 26 Similar to the patterning displayed by 4,6,8-trimethylazulene and C! (CN)" CF# , the crystal of 4,6,8-Trimethylazulene and C! (CN)% F( demonstrates a preference to stack of the carbon-carbon bond that rests between the two rings as opposed to stacking over the centroid of the more negatively charged ring. Unlike the crystallization with C! (CN)" CF# , however, this crystal does consist of a 1:1 stochiometric ratio. Figure 28: Unit Cell of 4,6,8-Trimethylazulene and C! (CN)% F( The unit cell of 4,6,8-Trimethylazulene and C! (CN)% F( confirms the 1:1 stochiometric composition of this cocrystal. Additionally, this unit cell confirms the preference of these compounds to stack face to face. This unit cell also demonstrates that each layer of cocrystal consists of approximately equal amounts of 4,6,8Trimethylazulene and C! (CN)% F( , as opposed to each individual layer consisting of only one compound. 27 Figure 29: IR Comparison of 4,6,8-Trimethylazulene and C! (CN)" CF# as Singular Crystals and Co-crystallized. In comparing the IRs of 4,6,8-trimethylazulene and C! (CN)" CF# there are three regions to pay attention to. First, the aromatic region is very evident in the azulene derivative. When co-crystallized, the aromatic region (around 3000 cm-1) is reduced in 28 intensity. The second in the C-N stretch of the C! (CN)" CF# . In the single crystal, the C-N stretch ranges from approximately 1975 cm-1 to 2400 cm-1. In the cocrystal, the C-N stretch is shifted. Finally, the fingerprint region of both single crystals is visually combined in the cocrystal, with prominent peaks at 1700 cm-1 and 1300 cm-1. The variations in intensities of the C-N stretch, aromatic region, and the combination of the fingerprint region in the cocrystal IR are all indicative of a successful cocrystal. Figure 30: UV-Vis Spectra of 4,6,8-Trimethylazulene and C! (CN)" CF# UV-Vis Spectra of 4,6,8-trimethylazulene and C! (CN)" CF# was completed by varying the concentration of C! (CN)" CF# in a set concentration of 4,6,8trimethylazulene. The light blue peak corresponds to only the 4,6,8-trimethylazulene, and the red peak corresponds to only C! (CN)" CF# . The mustard, indigo, pink, and deep purple peaks correspond to solutions with an identical concentration of 4,6,8trimethylazulene and an increasing concentration of C! (CN)" CF# . The amplification of 30 Figure 33: Unit Cell of Guaiazulene and C! (CN)" CF# Guaiazulene and C! (CN)" CF# demonstrate parallel stacking of a 1:1 cocrystal. When comparing the centroid distances of the five-member and seven-membered rings of the guaiazulene to the C! (CN)" CF# , the centroid of the five-membered ring should coordinate most closely. Contrary to this hypothesis, however, the centroid of the sevenmembered ring coordinates most closely. As with the 4,6,8-trimethylazulene the C! (CN)" CF# most closely coordinates with the carbon-carbon bond between the two rings. This implies that the electronics of these compounds is not the determining factor in coordination upon crystallization. Unlike the cocrystal of 4,6,8-trimethylazulene and C! (CN)" CF# , though, the trifluoromethyl group of the C! (CN)" CF# seems to prefer a single configuration, likely due to the steric hindrance presented by the isopropyl group on the seven-membered ring of the guaiazulene. 31 Figure 34: IR Comparison of Guaiazulene and C! (CN)" CF# as Singular Crystals and Co-crystallized. In comparing the IRs of guaiazulene and C! (CN)" CF# there are three regions to pay attention to. First, the aromatic region is very evident in the guaiazulene. When cocrystallized, the aromatic region (around 3000 cm-1) is reduced in intensity. The second 32 in the C-N stretch of the C! (CN)" CF# . In the single crystal, the C-N stretch ranges from approximately 1975 cm-1 to 2400 cm-1. In the cocrystal, the C-N stretch is shifted towards higher wavenumbers and amplified. Finally, the fingerprint region of both single crystals is visually combined in the cocrystal, with prominent peaks at 1700 cm-1 and 1300 cm-1. The variations in intensities of the C-N stretch, aromatic region, and the combination of the fingerprint region in the cocrystal IR are all indicative of a successful cocrystal. Figure 35: UV-Vis Spectra of Guaiazulene and C! (CN)" CF# UV-Vis Spectra of guaiazulene and C! (CN)" CF# by varying the concentration of C! (CN)" CF# in a set concentration of guaiazulene. The pink peak corresponds to only the guaiazulene, and the deep purple peaks correspond to solutions with an identical concentration of guaiazulene and an increasing concentration of C! (CN)" CF# . The solo C! (CN)" CF# peak can be referenced in Figure 25. Despite the additional peak in the 33 C! (CN)" CF# at approximately 500 nm (Figure 25), that peak is non-existent in the mixed C! (CN)" CF# , and guaiazulene. Amplification of the other C! (CN)" CF# is observed, though markedly less so than when mixed with the 4,6,8-trimethylazulene. The guaiazulene peak at 600 nm is also amplified when mixed with the C! (CN)" CF# , despite the concentration of guaiazulene remaining identical in all samples. Unlike the mixture of 4,6,8-trimethylazulene and C! (CN)" CF# , however, there is no increase in the range of wavelength detected by the spectrometer. While there is no increase in wavelength range, the amplification of all peaks implies that guaiazulene and C! (CN)" CF# interact prior to crystallization, while still in solvent. Platinum Cocrystals Unfortunately, despite the synthesis of multiple platinum complexes, only one generated crystal that could be analyzed using and x-ray diffractometer. The other either generated complexes that were too soft to undergo this type of analysis or yielded single crystals of the original starting complexes. As such, only benzoquinoline (Pt)2,2,6,6tetramethyl-3,5-heptanedione is discussed in the following section. Figure 36: Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and C! (CN)$ F% 35 Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and C! (CN)% F( yielded a cocrystal that demonstrated parallel stacking. Unexpectedly, the platinum complex did not stack with the platinum atom directly over the center of the anionic hole in C! (CN)% F( , which would fit with the work completed previously by the Richmond Group, but instead coordinates the carbon in Ring 3 closest to the platinum atom closest to the anionic hole in C! (CN)% F( . This means that the 𝑑$ % orbital of Pt(II) is not aligned with the anionic hole in C! (CN)% F( , as it does with C! (CN)( 𝐶F% , and C! (CN)" CF# .7 Despite this difference, it is worth noting that the carbon the anionic hole of C! (CN)% F( most aligns with is likely more negative, given the similarity of benzoquinoline(Pt) 2,2,6,6-tetramethyl-3,5-heptanedione with 2-phenylpyridine(Pt)acetylacetone, which has previously been electronically mapped by Anton V. Rozhkov et. al.15 Upon examination, the distances between some the fluorine atoms and nitrile groups on the cyanocarbon to in plane hydrogens on the platinum complex range in distance from 2.6 Å to 3.1 Å. Each plane also demonstrates that the molecules assume a chevron type of patterning. The distance between each plane is approximately 3.2 Å to 3.3 Å, and the out of plane distance of one of the methyl hydrogens is 2.1 Å. Though the lack of interaction between the 𝑑$ % orbital and the anionic hole of C! (CN)% F( is mildly confusing, especially given the geometry of that orbital, but the steric hinderance of the tert-butyl groups on the ACAC complex and the patterning of the cocrystal might partially explain some of that offset. It is also worth noting, the the distances between hydrogens and fluorine and hydrogens and nitrile groups mirror hydrogen-type bonding. 36 Figure 39: IR Comparison of Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and C! (CN)% F( as Singular Crystals and Co-crystallized. 37 When comparing the IRs of benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5heptanedione and C! (CN)% F( , there are two regions to pay attention to most. First, the aromatic region (around 3000 cm-1) is mildly reduced in intensity in the cocrystal when compared to the platinum complex alone. Secondly, the solo IR of C! (CN)% F( displays a very prominent peak at 2252 cm-1. This peak greatly decreases in intensity, and the C-N stretch shifts towards lower wavenumbers. Interestingly, the remainder of the C-N stretch is amplified. Normally, the fingerprint regions of these complexes would also be compared with one another; however, the fingerprint region of the quite busy, making a direct comparison between the two too subjective to be of much use. Regardless, the change in amplification and shift of the aromatic and C-N stretches demonstrates that a successful cocrystal was created. General Results Cocrystals and single compounds were analyzed using a Nicolet ATR is50 infrared spectrophotometer. For each azulene derivative – cyanocarbon cocrystal and each platinum (II) complex – cyanocarbon cocrystal, the peak that needed to be the most monitored was the C-N stretch peak, which is very weak in every IR. This peak generally appears between 2400 cm-1 and 2200 cm-1. This peak is primarily monitored because when a cyanocarbon interacts with an azulene derivative or platinum (II) complex, these peaks shift or alter in intensity. 38 Table 1: Compounds and Their Relative C-N Stretch C-N Stretch (cm-1) Compound Name C! (CN)" CF# 2198 C! (CN)% F( 2252 4,6,8-Trimethylazulene with C! (CN)" CF# 2226 Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione and 2245 C! (CN)% F( While IR peak shifts are important, it is also important to analyze and understand the distances between the centroids of each ring. When looking at this data, it would be assumed that the distances between more negative rings and the anionic hole of the fluorinated cyanocarbons would be shorter than distances between more positive rings and the anionic hole of fluorinated cyanocarbons. Interestingly enough, with the azulene derivatives, the exact opposite is true, with more positive rings having centroids that coordinate more closely with the anionic hole of the fluorinated cyanocarbon. Table 2: Distances Between Centroids Compound Name Distance (Centroid/Centroid) 4,6,8-Trimethylazulene (A7) and C! (CN)" CF# 3.560 Å / 3.488 Å 4,6,8-Trimethylazulene (A5) and C! (CN)" CF# 3.545 Å / 3.540 Å 4,6,8- Trimethylazulene (A7) and C! (CN)% F( 3.501 Å 4,6,8- Trimethylazulene (A5) and C! (CN)% F( 3.628 Å 39 Guaiazulene (GA7) and C! (CN)" CF# 3.479 Å Guaiazulene (GA5) and C! (CN)" CF# 3.612 Å Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5- 4.706 Å heptanedione (Ring 1) with C! (CN)% F( Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5- 4.208 Å heptanedione (Ring 2) with C! (CN)% F( Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5- 3.660 Å heptanedione (Ring 3) with C! (CN)% F( Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5- 3.549 Å heptanedione (Bz Pt Ring) with C! (CN)% F( Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5- 5.066 Å heptanedione (Pt ACAC Ring) with C! (CN)% F( When comparing the distances in Table 2 and Table 3, it is also worth noting that the distances between the anionic hole and the carbon-carbon bond between rings (or in the case of the platinum complex, the carbon-platinum bond) is generally shorter than the distance between each centroid. This was initially an unexpected result, but after some consideration, it would seem that the electron density of the azulene complexes in particular is higher across those carbon-carbon bonds than throughout the rest of the molecule, which would explain the proclivity of the anionic hole of the fluorinated cyanocarbon to form the closest connection to that bond. For azulene derivatives in particular, with one ring being generally thought of as positive and the other as negative (so that azulene derivatives can be thought of as 40 aromatic complexes), the bridge between those two rings might be carrying more electrons in general than the rest of the carbons in the electron sharing pi system of the ring. Mapping the electron densities of these complexes would be an interesting avenue of research for future projects and might contribute to the currently limited understanding we have of azulene and azulene derivative complexes. Table 3: Distance Between Fluorinated Cyanocarbons and Closest Bonds Compounds Distance (Centroid/Bond) 4,6,8-Trimethylazulene (Top) and C! (CN)" CF# 3.406 Å / 3.467 Å 4,6,8-Trimethylazulene (Bottom) and C! (CN)" CF# 3.435 Å / 3.384 Å 4,6,8- Trimethylazulene and C! (CN)% F( 3.430 Å / 3.495 Å Guaiazulene and C! (CN)" CF# 3.531 Å / 3.341 Å Benzoquinoline (Pt)2,2,6,6-tetramethyl-3,5-heptanedione 3.413 Å / 3.549 Å and C! (CN)% F( Finally, it is worth noting that each cocrystal stacks using a face-to-face stacking pattern. This is not the case for individual crystals. Individual crystals stack using a face to edge motif, as demonstrated by the unit cell of singular 4,6,8-Trimethylazulene. This change in stacking motif further demonstrates the change in properties of cocrystals as opposed to singular crystals. 41 Figure 40: Unit Cell of Single 4,6,8-Trimethylazulene It can also be observed that this arrangement of 4,6,8-trimethylazulene exists as the lowest energy conformer.11 This configuration, the lowest energy conformer, points to the increased importance of Van der Waals forces, and the decreased importance of charge-transfer interactions. 42 CONCLUSION AND FUTURE DIRECTIONS Throughout this thesis, an intense exploration of C! (CN)" CF# was completed, and it was demonstrated that there is conclusively an anionic hole at the center of the C! (CN)" CF# ring, making it an ideal compound for creating a new class of chargetransfer complexes. It was noted, though, that despite its electronic properties, when crystallized with azulene derivatives, Van der Waals forces played a more significant role in coordination patterns than electronics of these molecules, perhaps patterning what we would expect given the known lowest energy conformer of singularly crystallized azulene molecules. Furthermore, five new cocrystals were synthesized and analyzed. It has been determined that although the electronics of these cocrystals influence crystallization behavior, it is likely not the primary determining factor, unless the electronic density of azulene and azulene derivatives is different than traditionally thought. Future research should include mapping the electron density of azulene and azulene derivatives. It should also include potential cocrystallization with a large number of benzene-type molecules packed with both electron withdrawing groups and electron donating groups to analyze the different coordinating properties of these molecules. Future research should also quantitively compare naphthalene with azulene, and how they cocrystallize with one another. Naphthalene is an isomer of azulene but does not share the same theoretical electronic properties. Completing a comparison between naphthalene and azulene could yield further insight into some of the innate properties of each of these compounds. 43 It was interesting to note that the 𝑑$ % orbital of platinum did not coordinate directly over the anionic hole of C! (CN)% F( , despite previous research indicating that this is the type of patterning that would be expected. In this particular case, it appears as if steric hinderance played a role in the inability of the 𝑑$ % orbital to line up with the anionic hole of C! (CN)% F( . Future research comparing platinum complexes with bulky and not bulky ACAC complexes should be completed. Outside of furthering this type of research in the academic silo in which it exists, it might be worth exploring some of the cocrystals through an industrial and commercial lens. Historically, azulene has proven safe, if not helpful, when ingested by humans.8 Because of azulene and azulene derivatives unique electronic properties, it may well serve as the optimal molecule to cocrystallize medications that are insoluble in water and may serve as a very unique and useful drug delivery mechanism. This route of research must be further explored. Historically, platinum complexes have been used in electronic and medications. While research into future cancer fighting medications using platinum compounds should be continued, future research should also analyze how platinum ligands might be useful in clearing up environmental toxins (of which many are positively and negatively charged), as platinum is already used to help mitigate air pollution as it is present in catalytic converters of vehicles. Future work should analyze whether the use of platinum as a catalyst to mitigate air pollution could be applied to toxins in water and soil when new ligands are synthesized. Ultimately, cocrystals are still a very underexplored component of chemistry, and they have many uses in a wide variety of fields including medicine, agrochemistry, 44 electronics, an environmental health to name a few. While they can be frustrating to synthesize, as some are quite finnicky and require unique solvents, cocrystals also help us understand some of the chemical properties of each of its substrates, and is well worth the time and effort. 45 REFERENCES 1. Montgomery, L. (2023). Creating a New Class of Cyanocarbons with Unexplored Chemistry. A Senior Honors Thesis. 2. K.P Goetz, D. Vermeulen, M.E. Payne, C. Kloc, L.E. McNeil, and O.D. Jurchescu, Charge Transfer Complexes: New Perspective on an Old Class of Compounds, The Royal Society of Chemistry, 2014, 2, 3065-3076. 3. F.H. Herbstein, Crystalline Molecular Complexes and Compounds: Structure and Principles, Oxford University Press, New York, 2005 4. Stahly, G.P. A Survey of Cocrystals Reported Prior to 2000. Crys.Growth Des. 2009, 9 (10), 4212-4229. https://doi.org/10.1021/cq900873t. 5. Schmidt, G. M. J. “Topochemistry. Part III. The Crystal Chemistry of Some TransCinnamic Acids.” J. Chem. Soc. (Resumed) 1964, 0, 385. 6. Childs, S.L.; Zaworotko, M.J. The Reemergence of Cocrystals: The Crystal-Clear Writing Is on the Wall. Cryst. Growth Des. 2009, 9 (10), 4208-4211. https://doi.org/10.1021/cq901002y. 7. Aakeröy, C.B.; Sinha, A.S. Cocrystals: Introduction and Scope. In Co-crystals: Preparation, Characterization and Applications; Aakeröy, C.B.; Sinha, A.S., Eds.; Royal Society of Chemistry: Cambridge, 2018; Chapter 1 pp 1-26. https://doi.org/10.1039/9781788012874. 8. C.W. Pouton, Eur. J. Pharm. Sci., 2006, 29, 278-287 9. Kozuch, S. (2016). Should “anion–π interactions” be called “anion–σ interactions”? A revision of the origin of some hole-bonds and their nomenclature. Physical Chemistry Chemical Physics, 18, 30366-30369. 46 10. Lutz, K. Discovery of Platinum (II) Cocrystals with Highly Fluorinated Cyanocarbons. Senior Honors Thesis, the University of Utah, May 2023. Available online: https://collections.lib.utah.edu/ark:/87278/s6hh41zo (accessed April 5, 2024). 11. Piancenza, M.; Grimme, S. Van der Waals Complexes of Polar Aromatic Molecules: Unexpected Structures for Dimers of Azulene. Contribution from the Theoretische Organische Chemie, Organisch-Chemisches, Institut der Universitat Munster, Conrrensstrasse 40, D-48149 Munster, Germany. Received June, 2, 2005; made available on the web September 28, 2005 12. Bakun, P.; Czarczvnska-Goslinska, B.; Goslinski, T.; Lijewski, S. In vitro and in vivo biological activities of azulene derivatives with potential applications in medicine. Med. Chem. Res. 2021, 30 (4), 834-846. https://doi.org/10.1007/s00044-02102701-0. https://doi.org/10.1007/s00044-021-02701-0. 13. Deschamps, J.R. “X-Ray Crystallography of Chemical Compounds.” Life Sciences, 2010, 86 (15-16), 585-589. DOI: 10.1016/j.lfs.2009.02.028. PubMed PMID: 19303027. PubMed Central PMCID: PMC2848913. 14. Quertinmont, J.; Leyssens, T.; Wouters, J.; Champagne, B. "Unraveling the Effects of Co-Crystallization on the UV/Vis Absorption Spectra of an N-Salicylideneaniline Derivative: A computation RI-CC2 Investigation.” Molecules, 2020, 25 (19), 4512. DOI: 10.3390/molecules25194512. 15. Bhalla, Y.; Chadha, K.; Chadha, R.; Karan, M. "Daidzein Cocrystals: An Opportunity to Improve Its Biopharmaceutical Parameters.” Heliyon, 2019, 5(11), e02669. DOI: 10.1016/j.heliyon. 2019.e02669 16. G. Beck, Fluoromethylated polycyanobenzenes, their alkali metal cyanide adducts, 47 processes for their preparation and use of the fluoromethylated polycyanobenzenes, 1992, 5175336, United States Patent. 17. Garst, M.E.; Hochlowski, J.; Ill Douglass, J.G.; Sasse, S. The synthesis of 4,6,8Trimethylazulene: an organic laboratory experiment. J. Chem. Educ. 1983, 60 (6), 510. https://doi.org/10.1021/ed060p510 18. Hudson, Z.M.; Blight, B.A.; Wang, S. Efficient and high yield one-pot synthesis of cyclometalated platinum (II) b-diketonates at ambient temperature. Org. Lett. 2012, 14 (7), 1700-1703. https://doi.org/10.1021/ol300242f 19. Anton V. Rozhkov, Ivan V. Ananyev, Rosa M. Gomila, Antonio Frontera, and Vadim Yu. Kukushkin. Inorganic Chemistry 2020 59 (13), 9308-9314. DOI: 10.1021/acs.inorgchem.0c01170 48 Name of Candidate: Anneke E. Enquist Date of Submission: April 30, 2024 49 APPENDIX A: DETAILS OF X-RAY CRYSTALLOGRAPHIC STRUCTURES DETERMINED BY DR. RYAN VANDERLINDEN, UNIVERSITY OF UTAH, X-RAY CORE FACILITY The X-Ray Diffractometer used in this research was funded by the Office of the Director, National Institute of Health of the National Institute of Health under Award Number S10OD030326. The content is solely the responsibility of the authors and does not necessarily represent the official view of the National Institute of Health wit_20231109TR Sample ID: wit_20231109TR R1=3.70% Crystal Data and Experimental Compound Experimental. Single None None None ? -shaped crystals of wit_20231109TR were obtained by recrystallisation from .... A suitable crystal ? ×? ×? mm3 was selected and mounted on a suitable support on an ? diffractometer. The crystal was kept at a steady T = 100(2) K during data collection. The structure was solved with the ? structure solution program using the Intrinsic Phasing solution method and by using ? as the graphical interface. The model was refined with version 2018/3 of ShelXL-2018/3 (Sheldrick, 2018) using Least Squares minimisation. Crystal Data. C20H16F3N5O8, Mr = 505.36, monoclinic, P21/c (No. 14), a = 8.1465(2) Å, b = 15.2818(5) Å, c = 19.2402(7) Å,  = 98.759(3)°,  =  = 90°, V = 2367.34(13) Å3, T = 100(2) K, Z = 4, Z' = 1, (CuK) = 1.093, 4915 reflections measured, 2255 unique (Rint = 0.0116) which were used in all calculations. The final wR2 was 0.1056 (all data) and R1 was 0.0370 (I > 2(I)). wit_20231109TR Formula C20H16F3N5O8 Dcalc./ g cm-3 1.418 1.093 /mm-1 Formula Weight 505.36 Colour None None None Shape ? Size/mm3 ? ×? ×? T/K 100(2) Crystal System monoclinic Space Group P21/c a/Å 8.1465(2) b/Å 15.2818(5) c/Å 19.2402(7) 90 /° 98.759(3)  /° 90 /° V/Å3 2367.34(13) Z 4 Z' 1 Wavelength/Å 1.54184 Radiation type CuK 3.711 min/° 51.980 max/° Measured Refl. 4915 Independent Refl. 2255 Reflections with I > 2013 2(I) Rint 0.0116 Parameters 333 Restraints 0 Largest Peak 0.365 Deepest Hole -0.169 GooF 1.068 wR2 (all data) 0.1056 wR2 0.1024 R1 (all data) 0.0414 R1 0.0370 Structure Quality Indicators Reflections: Refinement: Experimental Extended. A None None None ? -shaped crystal with dimensions ? ×? ×? mm3 was mounted on a suitable support. Data were collected using an ? diffractometer operating at T = 100(2) K. Data were measured using CuK radiation. The maximum resolution that was achieved was  = 51.980° (0.98 Å). The diffraction pattern was indexed and the unit cell was refined on ? reflections, 0% of the observed reflections. Data reduction, scaling and absorption corrections were performed . The final completeness is 85.10 % out to 51.980° in . A ? absorption correction was performed using ? The absorption coefficient  of this material is 1.093 mm-1 at this wavelength ( = 1.542Å) and the minimum and maximum transmissions are 0 and 0. The structure was solved and the space group P21/c (# 14) determined by the ? structure solution program using Intrinsic Phasing and refined by Least Squares using version 2018/3 of ShelXL-2018/3 (Sheldrick, 2018). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model. Hydrogen atom positions were calculated geometrically and refined using the riding model. Table 1: Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å 2×103) for wit_20231109TR. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom F8 F9 F10 O21 O25 O29 O31 O23 O27 O33 O35 N16 N14 N18 C1 C5 N20 C6 N12 C4 C2 C30 C22 C3 C26 C15 C19 x 6691.4(19) 4657(2) 7055(2) 5330(2) 10034(2) 11127(2) 9153(2) 3737(2) 11762(2) 2772(2) 4514(2) 10475(3) 4316(4) 11840(3) 6752(3) 8873(3) 8740(3) 8357(3) 2741(3) 7826(3) 5719(3) 10075(3) 4590(3) 6238(3) 10980(3) 9503(4) 8342(3) y 6961.7(11) 6126.3(11) 5581.3(11) 7925.4(12) 4831.7(12) 3548.1(12) 4574.7(12) 9115.1(12) 3694.1(12) 9016.9(13) 7886.9(12) 7148.4(17) 5598.6(17) 7215.5(16) 6312.3(16) 6653.8(16) 6543.5(16) 6614.6(16) 5428.6(16) 6398.2(16) 6040.6(16) 3984.9(18) 8547.7(18) 6083.2(16) 4342.1(18) 6904.9(18) 6467.3(17) z 5287.8(8) 5416.6(9) 5365.3(9) 7539.1(10) 8031.9(10) 6788.0(10) 6657.6(10) 7507.6(10) 8167.5(10) 6107.7(11) 6172.4(10) 5895.1(14) 8489.3(16) 7874.1(14) 6410.1(15) 7404.0(15) 9201.4(16) 6678.1(15) 6517.8(14) 7872.6(15) 6876.9(15) 6408.4(15) 7845.5(15) 7606.2(15) 8414.5(15) 6224.7(17) 8612.1(18) Ueq 37.2(5) 45.5(5) 52.0(6) 28.5(5) 31.2(5) 30.0(5) 29.7(5) 30.2(5) 34.6(6) 35.9(6) 34.2(5) 36.6(7) 42.6(8) 40.0(7) 21.3(7) 21.7(7) 43.6(8) 21.5(7) 42.8(7) 21.3(7) 21.6(7) 26.7(7) 24.8(7) 22.3(7) 25.9(7) 26.6(8) 26.9(8) Atom C34 C13 C7 C17 C11 C28 C24 C32 C36 x 3527(3) 5156(4) 6274(3) 10533(4) 4054(4) 11319(4) 4900(3) 9763(4) 3106(4) y 8384.3(19) 5817.1(18) 6248.8(18) 6961.7(17) 5708.6(18) 4431.7(19) 8506.0(18) 3878(2) 8330(2) z 5825.2(15) 8092.9(18) 5618.5(16) 7667.9(15) 6654.3(15) 9190.3(15) 8622.9(14) 5636.7(15) 5050.4(16) Ueq 28.2(7) 29.3(8) 30.1(8) 26.2(7) 29.0(8) 33.0(8) 30.5(8) 37.5(8) 39.9(8) Table 2: Anisotropic Displacement Parameters (×104) wit_20231109TR. The anisotropic displacement factor exponent takes the form: -22[h2a*2 × U11+ ... +2hka* × b* × U12] Atom F8 F9 F10 O21 O25 O29 O31 O23 O27 O33 O35 N16 N14 N18 C1 C5 N20 C6 N12 C4 C2 C30 C22 C3 C26 C15 C19 C34 C13 C7 C17 C11 C28 C24 C32 C36 U11 39.5(10) 38.5(11) 72.4(13) 28.9(11) 32.1(11) 29.2(11) 29.0(11) 30.6(11) 41.5(12) 38.8(12) 33.6(11) 35.1(16) 40.9(17) 29.9(16) 24.9(16) 21.1(16) 54.4(18) 21.3(16) 31.2(16) 22.8(16) 22.1(16) 24.3(16) 19.6(15) 23.4(16) 23.5(15) 27.4(19) 27.3(17) 25.5(16) 29.5(19) 29.2(18) 29.0(19) 27.5(19) 34.4(17) 30.1(17) 40.2(19) 41.3(19) U22 42.5(11) 58.1(12) 45.7(12) 28.0(11) 29.3(11) 27.8(11) 34.8(12) 24.6(11) 31.5(12) 32.8(12) 36.6(12) 39.5(17) 37.8(17) 38.3(16) 14.8(15) 17.4(15) 39.9(17) 18.1(15) 37.9(16) 17.6(15) 16.4(15) 25.5(17) 21.4(17) 14.3(15) 24.3(17) 22.9(17) 20.5(17) 27.7(18) 22.0(17) 22.4(18) 22.5(16) 23.7(17) 36.1(18) 32.9(18) 43(2) 45(2) U33 27.1(10) 34.0(11) 33.3(11) 26.6(12) 30.2(13) 31.3(12) 24.7(12) 33.9(13) 29.3(13) 32.4(13) 29.8(13) 34.7(19) 50(2) 47.5(18) 22.9(19) 25(2) 33(2) 25(2) 55(2) 22(2) 25(2) 30(2) 33(2) 30(2) 29(2) 26(2) 32(2) 31(2) 34(2) 37(2) 25.9(19) 33(2) 26.6(19) 27(2) 28(2) 32(2) U23 6.1(8) 1.1(8) -10.9(8) 0.0(9) 1.4(9) 0.2(9) 0.8(9) -1.7(9) 2.3(9) -0.6(10) -1.4(9) 0.0(13) 6.5(14) -1.8(12) -1.8(12) -1.3(12) -0.5(13) 1.3(12) 4.8(13) 2.6(12) -1.1(12) -1.7(14) -4.2(14) 2.7(12) 1.4(14) -3.4(14) 2.1(13) 2.0(15) 1.2(14) -1.8(15) 1.5(12) 0.3(13) 1.2(13) -2.9(13) -1.5(14) 6.6(15) U13 -3.4(8) -13.9(9) -6.4(10) -2.4(10) -2.0(10) -0.7(10) 2.2(10) 0.3(10) 0.4(11) -6.3(11) -3.9(10) 4.0(15) 8.8(16) -7.2(14) -0.5(15) -2.4(15) -3.3(15) 3.1(15) -6.7(14) 0.0(15) 0.5(15) 5.2(15) 2.6(14) 5.6(16) 2.0(14) -6.2(18) 0.6(16) 2.7(15) -1.0(19) -1.3(16) 0.6(15) -3.0(15) -1.5(15) 0.7(14) 2.0(16) 1.3(16) U12 -1.2(8) -12.3(8) 20.6(10) 5.7(9) 6.3(9) 5.2(9) 5.1(9) 5.3(9) 11.0(10) 8.8(10) 11.2(10) -5.6(13) 1.3(13) -5.5(13) 3.3(12) 2.0(12) -1.9(13) 2.0(12) -7.3(13) 3.1(12) 0.4(12) -6.5(14) -4.7(13) 2.2(12) -2.8(14) 1.6(14) 0.8(12) -1.5(14) 2.6(14) 4.2(14) 1.2(13) 0.1(14) -2.7(13) -3.6(13) 5.1(14) 8.2(15) Table 3: Bond Lengths in Å for wit_20231109TR. Atom F8 F9 F10 O21 O25 O29 O31 O23 Atom C7 C7 C7 C22 C26 C30 C30 C22 Length/Å 1.331(3) 1.329(3) 1.333(3) 1.313(3) 1.234(3) 1.234(3) 1.310(3) 1.233(3) Atom O27 O33 O35 N16 N14 N18 C1 C1 Atom C26 C34 C34 C15 C13 C17 C2 C6 Length/Å 1.306(3) 1.308(3) 1.227(3) 1.149(4) 1.149(4) 1.146(3) 1.385(4) 1.409(4) Atom C1 C5 C5 C5 N20 C6 N12 C4 Atom C7 C4 C6 C17 C19 C15 C11 C3 Length/Å 1.517(4) 1.388(4) 1.397(4) 1.449(4) 1.137(4) 1.441(5) 1.145(4) 1.402(4) Atom C4 C2 C2 C30 C22 C3 C26 C34 Atom C19 C3 C11 C32 C24 C13 C28 C36 Atom C4 C4 C2 O25 O25 O27 N16 N20 O35 O35 O33 N14 F9 F9 F8 F9 F8 F10 N18 N12 Atom C3 C3 C3 C26 C26 C26 C15 C19 C34 C34 C34 C13 C7 C7 C7 C7 C7 C7 C17 C11 Length/Å 1.425(4) 1.404(4) 1.450(4) 1.477(4) 1.480(4) 1.439(5) 1.482(4) 1.480(4) Table 4: Bond Angles in ° for wit_20231109TR. Atom C2 C2 C6 C4 C4 C6 C5 C5 C1 C5 C5 C3 C1 C1 C3 O29 O29 O31 O23 O23 O21 Atom C1 C1 C1 C5 C5 C5 C6 C6 C6 C4 C4 C4 C2 C2 C2 C30 C30 C30 C22 C22 C22 Atom C6 C7 C7 C6 C17 C17 C1 C15 C15 C3 C19 C19 C3 C11 C11 O31 C32 C32 O21 C24 C24 Angle/° 118.9(2) 123.0(2) 118.1(3) 121.1(2) 119.8(2) 119.1(3) 120.1(3) 117.9(2) 122.0(3) 118.9(2) 120.7(2) 120.4(3) 120.9(2) 123.1(2) 115.9(3) 122.8(3) 122.2(3) 115.1(2) 122.2(3) 124.0(3) 113.8(2) Atom C2 C13 C13 O27 C28 C28 C6 C4 O33 C36 C36 C3 F8 F10 F10 C1 C1 C1 C5 C2 Angle/° 120.1(3) 118.8(3) 121.1(2) 122.5(3) 123.2(3) 114.2(2) 176.3(3) 178.3(3) 122.8(3) 123.1(3) 114.1(2) 178.8(3) 106.8(2) 107.0(2) 106.3(3) 113.2(3) 112.5(2) 110.6(2) 179.1(3) 176.0(3) Table 5: Hydrogen Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for wit_20231109TR. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom H21 H31 H27 H33 H28A H28B H28C H24A H24B H24C H32A H32B H32C H36A H36B H36C x 5070.16 9373.36 11529.29 3057.64 12507.04 10990.41 10682.09 4587.85 4235.89 6080.94 10353.5 8568.22 10158.41 1896.42 3538.82 3603.08 y 7966.94 4583.03 3684.23 9011.05 4536.09 3892.87 4925.25 7926.39 8954.19 8609.64 4335.07 3925.43 3301.67 8346.28 7782.06 8826.51 z 7100.78 7098.45 7726.94 6545.98 9339.12 9408.76 9335.78 8777.45 8815.71 8790.45 5417.2 5468.93 5511.76 4916.38 4885.82 4835.96 Ueq 43 45 52 54 50 50 50 46 46 46 56 56 56 60 60 60 Citations Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H. (2009), J. Appl. Cryst. 42, 339-341. Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8. Sheldrick, G.M. (2015). Acta Cryst. C71, 3-8. 20231006TR_Purple ? (d, operator_header)Sample ID: R1=5.61% 20231006TR_Purple Crystal Data and Experimental Compound Experimental. Single violet plate-shaped crystals of 20231006TR_Purple were obtained by recrystallisation from .... A suitable crystal 0.04×0.04×0.01 mm3 was selected and mounted on a suitable support on an XtaLAB Synergy R, DW system, HyPix diffractometer. The crystal was kept at a steady T = 100.00(11) K during data collection. The structure was solved with the ShelXT (Sheldrick, 2015) structure solution program using the Intrinsic Phasing solution method and by using Olex2 (Dolomanov et al., 2009) as the graphical interface. The model was refined with version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015) using Least Squares minimisation. Crystal Data. C13H14, Mr = 170.24, monoclinic, P21/c (No. 14), a = 8.0753(3) Å, b = 11.6839(5) Å, c = 10.4605(4) Å,  = 100.435(4)°,  =  = 90°, V = 970.64(7) Å3, T = 100.00(11) K, Z = 4, Z' = 1, (Cu K) = 0.485, 14213 reflections measured, 1820 unique (Rint = 0.0372) which were used in all calculations. The final wR2 was 0.1552 (all data) and R1 was 0.0561 (I > 2(I)). 20231006TR_Purp le Formula C13H14 Dcalc./ g cm-3 1.165 -1 0.485 /mm Formula Weight 170.24 Colour violet Shape plate Size/mm3 0.04×0.04×0.01 T/K 100.00(11) Crystal System monoclinic Space Group P21/c a/Å 8.0753(3) b/Å 11.6839(5) c/Å 10.4605(4) 90 /° ° 100.435(4) / ° 90 / V/Å3 970.64(7) Z 4 Z' 1 Wavelength/Å 1.54184 Radiation type Cu K 5.571 min/° ° 70.036 max/ Measured Refl. 14213 Independent Refl. 1820 Reflections with I > 1557 2(I) Rint 0.0372 Parameters 120 Restraints 0 Largest Peak 0.436 Deepest Hole -0.332 GooF 1.047 wR2 (all data) 0.1552 wR2 0.1486 R1 (all data) 0.0653 R1 0.0561 Structure Quality Indicators Reflections: Refinement: Experimental Extended. A violet plate-shaped crystal with dimensions 0.04×0.04×0.01 mm3 was mounted on a suitable support. Data were collected using an XtaLAB Synergy R, DW system, HyPix diffractometer operating at T = 100.00(11) K. Data were measured using  scans of 0.5° per frame for 4.0/16.0 s using Cu K radiation. The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) The maximum resolution that was achieved was  = 70.036° (0.82 Å). The diffraction pattern was indexed The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) and the unit cell was refined using CrysAlisPro (Rigaku, V1.171.42.93a, 2023) on 7388 reflections, 52% of the observed reflections. Data reduction, scaling and absorption corrections were performed using CrysAlisPro (Rigaku, V1.171.42.93a, 2023). The final completeness is 99.00 % out to 70.036° in . A multi-scan absorption correction was performed using CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023) using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. The absorption coefficient  of this material is 0.485 mm-1 at this wavelength ( = 1.542Å) and the minimum and maximum transmissions are 0.619 and 1.000. The structure was solved and the space group P21/c (# 14) determined by the ShelXT (Sheldrick, 2015) structure solution program using Intrinsic Phasing and refined by Least Squares using version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model. Hydrogen atom positions were calculated geometrically and refined using the riding model. _exptl_absorpt_process_details: CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023) using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. Table 1: Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å 2×103) for 20231006TR_Purple. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom C1 C5 C8 C6 C10 C7 C9 C4 C2 C11 C12 C3 C13 x 4400(3) 2917(2) 5929(3) 2872(2) 6051(2) 4246(2) 6693(2) 1536(3) 3781(3) 1195(3) 7082(3) 2080(3) 7274(3) y 4639.4(16) 4007.0(16) 3242.5(16) 3237.0(16) 4668.0(16) 2894.4(16) 4046.6(16) 4326.8(17) 5276.6(18) 2723.5(18) 2691.9(18) 5087.3(19) 5448.3(18) z 2569.1(18) 2895.2(18) 5048.9(18) 3916.5(18) 3242.3(19) 4843.6(18) 4353.6(18) 1959.5(19) 1437(2) 4036(2) 6184(2) 1083(2) 2742(2) Ueq 29.8(5) 28.9(5) 29.4(5) 29.1(5) 30.3(5) 29.1(5) 29.4(5) 33.8(5) 35.5(5) 37.3(5) 38.1(5) 38.0(5) 37.3(5) Table 2: Anisotropic Displacement Parameters (×104) 20231006TR_Purple. The anisotropic displacement factor exponent takes the form: -22[h2a*2 × U11+ ... +2hka* × b* × U12] Atom C1 C5 C8 C6 C10 C7 C9 C4 C2 C11 C12 C3 C13 U11 45.6(11) 38.8(11) 41.2(11) 39.0(11) 37.7(11) 41.7(11) 33.3(10) 33.0(10) 45.7(12) 38.5(11) 45.6(12) 47.0(12) 44.7(12) U22 20.2(9) 21.6(9) 20.5(9) 21.1(9) 22.3(9) 19.8(9) 23.8(10) 32.3(11) 29.8(11) 33.5(11) 30.6(11) 35.5(11) 30.7(11) U33 26.0(9) 27.0(9) 26.9(9) 28.7(9) 33.1(10) 27.2(9) 31.5(10) 35.5(10) 32.2(10) 41.2(11) 36.2(11) 29.0(10) 40.5(11) U23 -2.2(7) -5.0(7) -5.1(7) -5.0(7) -5.1(8) 0.3(7) -5.7(8) -2.8(8) 2.0(8) 2.7(9) 0.5(9) 1.9(8) -0.6(9) U13 13.0(8) 7.9(8) 6.9(8) 10.0(8) 12.2(8) 9.8(8) 6.6(8) 4.0(8) 10.1(9) 10.7(9) 2.3(9) 0.6(9) 17.9(9) U12 3.9(8) 3.8(8) 4.4(8) 2.3(8) 3.1(8) 1.5(8) 2.8(8) 2.5(8) 0.9(9) 1.1(9) 5.3(9) 8.9(9) -1.0(9) Table 3: Bond Lengths in Å for 20231006TR_Purple. Atom C1 C1 C1 C5 C5 C8 C8 Atom C5 C10 C2 C6 C4 C7 C9 Length/Å 1.499(3) 1.390(3) 1.412(3) 1.402(3) 1.395(3) 1.397(3) 1.398(3) Atom C8 C6 C6 C10 C10 C4 C2 Atom C12 C7 C11 C9 C13 C3 C3 Atom C7 C7 C1 C9 C9 C6 C10 C5 C3 C2 Atom C6 C6 C10 C10 C10 C7 C9 C4 C2 C3 Length/Å 1.513(3) 1.394(3) 1.506(3) 1.389(3) 1.506(3) 1.403(3) 1.374(3) Table 4: Bond Angles in ° for 20231006TR_Purple. Atom C10 C10 C2 C6 C4 C4 C7 C7 C9 C5 Atom C1 C1 C1 C5 C5 C5 C8 C8 C8 C6 Atom C5 C2 C5 C1 C1 C6 C9 C12 C12 C11 Angle/° 128.98(17) 125.02(19) 105.94(18) 128.45(18) 106.17(17) 125.37(19) 128.62(18) 116.09(18) 115.28(18) 117.81(18) Atom C5 C11 C13 C1 C13 C8 C8 C3 C1 C4 Angle/° 125.94(18) 116.24(17) 117.88(18) 126.15(19) 115.97(18) 130.78(18) 130.80(19) 108.85(18) 109.03(19) 109.99(18) Table 5: Hydrogen Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 20231006TR_Purple. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom H7 H9 H4 H2 H11A H11B H11C H12A H12B H12C H3 H13A H13B x 3997.72 7844.76 411.31 4434.56 410.7 1341.41 743.32 8225.3 6674.83 7093.01 1376.28 7333.32 8391.81 y 2329.94 4192.34 4071.54 5758.56 3335.42 2202.39 2298.74 2993.95 2863.78 1861.19 5422.09 5242.11 5367.56 z 5434.57 4699.11 1921.69 990.96 4162.84 4782.49 3241.89 6240.56 6990.08 6055.74 352.64 1843.3 3285.55 Ueq 35 35 41 43 56 56 56 57 57 57 46 56 56 Atom H13C x 6894.52 y 6242.82 z 2772 Ueq 56 Citations O.V. Dolomanov and L.J. Bourhis and R.J. Gildea and J.A.K. Howard and H. Puschmann, Olex2: A complete structure solution, refinement and analysis program, J. Appl. Cryst., (2009), 42, 339-341. 20231025TR_4,6,8-Trimethylazulene ? (d, operator_header)Sample ID: R1=5.83% 20231025TR_4,6,8-Trimethylazulene Crystal Data and Experimental Compound Experimental. Single dark red plate-shaped crystals of 20231025TR_4,6,8-Trimethylazulene were obtained by recrystallisation from .... A suitable crystal 0.09×0.05×0.03 mm3 was selected and mounted on a suitable support on an XtaLAB Synergy R, DW system, HyPix diffractometer. The crystal was kept at a steady T = 100.00(12) K during data collection. The structure was solved with the ShelXT (Sheldrick, 2015) structure solution program using the Intrinsic Phasing solution method and by using Olex2 (Dolomanov et al., 2009) as the graphical interface. The model was refined with version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015) using Least Squares minimisation. Crystal Data. C38H26F3N5, Mr = 611.60, monoclinic, P21/c (No. 14), a = 14.4532(3) Å, b = 15.3181(4) Å, c = 13.8719(3) Å,  = 96.219(2)°,  =  = 90°, V = 3053.10(12) Å3, T = 100.00(12) K, Z = 4, Z' = 1, (Cu K) = 0.759, 46275 reflections measured, 5798 unique (Rint = 0.0600) which were used in all calculations. The final wR2 was 0.1711 (all data) and R1 was 0.0583 (I > 2(I)). 20231025TR_4,6,8 -Trimethylazulene Formula C38H26F3N5 Dcalc./ g cm-3 1.331 -1 0.759 /mm Formula Weight 611.60 Colour dark red Shape plate Size/mm3 0.09×0.05×0.03 T/K 100.00(12) Crystal System monoclinic Space Group P21/c a/Å 14.4532(3) b/Å 15.3181(4) c/Å 13.8719(3) 90 /° ° 96.219(2) / ° 90 / V/Å3 3053.10(12) Z 4 Z' 1 Wavelength/Å 1.54184 Radiation type Cu K 3.076 min/° ° 70.061 max/ Measured Refl. 46275 Independent Refl. 5798 Reflections with I > 4449 2(I) Rint 0.0600 Parameters 515 Restraints 31 Largest Peak 0.603 Deepest Hole -0.216 GooF 1.028 wR2 (all data) 0.1711 wR2 0.1573 R1 (all data) 0.0769 R1 0.0583 Structure Quality Indicators Reflections: Refinement: Experimental Extended. A dark red plate-shaped crystal with dimensions 0.09×0.05×0.03 mm3 was mounted on a suitable support. Data were collected using an XtaLAB Synergy R, DW system, HyPix diffractometer operating at T = 100.00(12) K. Data were measured using  scans of 0.5° per frame for 10.0/40.0 s using Cu K radiation. The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) The maximum resolution that was achieved was  = 70.061° (0.82 Å). The diffraction pattern was indexed The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) and the unit cell was refined using CrysAlisPro (Rigaku, V1.171.42.93a, 2023) on 15865 reflections, 34% of the observed reflections. Data reduction, scaling and absorption corrections were performed using CrysAlisPro (Rigaku, V1.171.42.93a, 2023). The final completeness is 100.00 % out to 70.061° in . A gaussian absorption correction was performed using CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. The absorption coefficient  of this material is 0.759 mm-1 at this wavelength ( = 1.542Å) and the minimum and maximum transmissions are 0.728 and 0.943. The structure was solved and the space group P21/c (# 14) determined by the ShelXT (Sheldrick, 2015) structure solution program using Intrinsic Phasing and refined by Least Squares using version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model. Hydrogen atom positions were calculated geometrically and refined using the riding model. _exptl_absorpt_process_details: CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. Table 1: Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å 2×103) for 20231025TR_4,6,8-Trimethylazulene. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom C1 C2 F3A F3B F3C F3D F3E F3F N3B C4 C5A N6A x 7968.9(12) 8416.5(15) 7781.8(14) 9067(2) 8759(3) 8310(20) 9374(11) 8238(19) 8836(11) 7446.7(12) 7346.7(14) 7240.5(18) y 4266.8(14) 3591.4(15) 2979.4(18) 3141(2) 3886.5(19) 2772(10) 3679(19) 3688(19) 3247(11) 3988.2(13) 3072.1(15) 2366.9(15) z 8209.7(14) 8911.1(15) 9118.3(18) 8544.3(19) 9751(2) 8649(18) 8970(20) 9750(13) 9468(13) 7352.4(13) 7103.6(15) 6872.3(17) Ueq 31.4(4) 40.6(5) 47.1(8) 59.7(11) 68.6(13) 115(18) 114(12) 102(14) 38(4) 30.2(4) 38.3(5) 49.1(6) Atom F6A F6B F6C C7 C8 C10 C11 N12 F12C F12B F12A C13 C14 N15 C16 C17 N18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 N9 x 6680(12) 7665(12) 8086(13) 7005.0(12) 6482.3(13) 7089.7(12) 6655.4(14) 6335.1(14) 5960(30) 7171(17) 6260(30) 7627.5(12) 7719.1(14) 7778.2(13) 8059.1(12) 8584.8(14) 8978.8(13) 9382.5(14) 9807.8(16) 10272.2(16) 10164.8(15) 9618.3(13) 9372.1(14) 8803.8(14) 8362.4(14) 8389.5(15) 8848.1(15) 9752.1(18) 7803.1(17) 8747(2) 5392.6(13) 4893.1(14) 4705.1(15) 5056.4(16) 5493.7(14) 5904.6(16) 6386.5(16) 6568.2(14) 6264.1(14) 5720.0(13) 5807(2) 7123.3(17) 5469.6(17) 6077.5(12) y 2628(10) 2827(10) 2507(9) 4596.3(13) 4302.7(13) 5486.0(13) 6121.8(14) 6633.6(14) 6860(30) 6934(19) 6009(17) 5767.3(13) 6685.3(14) 7419.8(13) 5158.7(14) 5500.6(14) 5808.6(14) 5710.5(15) 6168.9(19) 5578(2) 4740(2) 4775.9(15) 4057.6(15) 4067.3(15) 4759.2(15) 5643.0(15) 6091.5(15) 3179.7(17) 4505(2) 7070.8(17) 5386.6(14) 5474.6(18) 4652(2) 4027.2(18) 4441.8(14) 4018.5(15) 4417.9(16) 5295.1(16) 6019.1(14) 6085.3(14) 3036.1(17) 5484(2) 6990.1(15) 4069.6(13) z 7152(14) 6190(11) 7629(12) 6701.7(13) 5816.4(14) 6900.7(13) 6235.3(15) 5715.8(15) 6470(20) 5860(20) 5250(20) 7750.3(13) 7951.8(15) 8099.5(14) 8403.5(13) 9268.7(14) 9940.6(13) 6446.9(15) 7254.0(18) 7898.5(18) 7528.9(17) 6626.2(14) 6031.1(16) 5147.8(15) 4631.0(14) 4860.3(15) 5652.2(16) 6355(2) 3690.8(16) 5642(2) 8257.1(14) 7330.5(16) 6947.3(18) 7611(2) 8445.2(16) 9266.4(17) 10076.9(17) 10298.0(14) 9742.9(15) 8852.6(15) 9301(2) 11258.5(16) 8503.9(18) 5108.7(12) Ueq 84(6) 74(5) 87(6) 29.5(4) 32.9(4) 29.3(4) 35.3(5) 48.9(5) 124(15) 92(9) 109(12) 30.3(4) 35.6(5) 45.4(5) 31.0(4) 35.2(5) 45.7(5) 37.6(5) 52.2(6) 59.1(8) 51.0(6) 36.9(5) 38.9(5) 39.6(5) 38.3(5) 40.5(5) 40.8(5) 56.0(7) 55.2(7) 60.4(7) 33.3(4) 46.0(6) 57.4(7) 54.4(7) 38.2(5) 44.1(6) 46.6(6) 39.7(5) 35.6(5) 34.2(5) 71.3(9) 61.0(8) 47.7(6) 42.3(5) Table 2: Anisotropic Displacement Parameters (×104) 20231025TR_4,6,8-Trimethylazulene. The anisotropic displacement factor exponent takes the form: -22[h2a*2 × U11+ ... +2hka* × b* × U12] Atom C1 C2 F3A F3B F3C F3D F3E F3F N3B C4 C5A N6A F6A U11 25.3(9) 35.8(11) 41.0(11) 45.8(15) 99(3) 180(40) 59(11) 100(20) 31(8) 26.8(9) 37.4(11) 55.6(15) 83(11) U22 40.4(11) 48.0(13) 48.3(15) 69(2) 50.3(16) 44(10) 110(20) 180(30) 30(9) 37.0(11) 42.4(13) 40.5(14) 48(9) U33 27.8(9) 36.8(12) 51.3(15) 67.7(17) 45.5(17) 100(20) 160(30) 23(10) 50(8) 26.6(9) 33.7(11) 49.1(13) 128(15) U23 -1.0(8) -5.2(10) 22.6(11) 30.6(15) 4.0(11) 8(10) 64(19) 49(14) 2(6) -1.4(8) 2.0(9) -3.8(11) -26(9) U13 0.6(7) -1.1(9) 2.2(9) 22.2(12) -42.1(19) -80(30) -36(14) 23(12) -12(6) 1.4(7) -1.8(8) -3.2(11) 44(10) U12 0.2(8) 0.0(9) 0.7(9) 32.5(14) 7.7(16) 15(14) 12(12) 80(20) -1(6) -2.6(7) -3.4(9) 0.7(11) -22(8) Atom F6B F6C C7 C8 C10 C11 N12 F12C F12B F12A C13 C14 N15 C16 C17 N18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 N9 U11 100(12) 116(14) 23.8(8) 31.6(10) 24.6(9) 32.5(10) 46.5(11) 130(30) 56(14) 170(30) 25.6(9) 33.7(10) 47.8(11) 23.7(9) 31.9(10) 43.5(10) 30.6(10) 39.7(12) 30.4(11) 30.7(11) 25.0(9) 33.5(10) 35.1(10) 31.6(10) 37.9(11) 42.2(11) 57.2(15) 44.5(13) 76.4(18) 24.1(9) 29.4(10) 29.3(11) 39.7(12) 30.3(10) 46.3(12) 47.7(12) 33.3(10) 34.4(10) 31.7(10) 90(2) 46.4(13) 53.1(13) 41.3(10) U22 58(9) 47(8) 38.9(11) 37.3(11) 37.5(11) 42.1(12) 51.7(13) 160(30) 89(19) 40(13) 37.4(11) 40.2(12) 41.9(11) 42.8(11) 43.9(12) 57.9(12) 48.6(12) 67.1(16) 108(2) 83.3(19) 54.6(13) 46.4(12) 49.9(13) 57.9(14) 54.0(13) 41.6(12) 55.1(15) 91(2) 47.2(15) 44.6(12) 70.9(16) 96(2) 59.6(16) 41.8(12) 38.7(12) 55.8(14) 61.9(14) 41.7(11) 38.6(11) 40.4(15) 110(2) 41.6(13) 53.4(12) U33 68(9) 89(12) 25.6(9) 29.4(10) 26.0(9) 30.6(10) 47.5(11) 90(20) 130(20) 100(20) 28.2(10) 32.7(10) 45.7(11) 26.1(9) 29.1(10) 33.5(10) 35.1(11) 51.3(14) 38.2(13) 37.9(12) 31.3(10) 38.2(11) 34.3(11) 26.3(10) 30.8(10) 41.3(12) 56.8(15) 29.8(11) 61.4(16) 31.5(10) 36.7(12) 45.3(14) 66.1(17) 44.4(12) 50.9(14) 38.9(12) 25.1(10) 31.3(10) 33.0(10) 91(2) 25.5(11) 49.0(13) 30.3(9) U23 -11(7) -9(8) -2.1(8) 0.6(8) 1.6(8) 0.2(9) 13.7(10) 10(20) 26(16) -9(13) -2.7(8) -2.3(9) -3.5(9) -3.5(8) -2.8(9) -8.2(9) -3.9(9) -16.5(12) -14.2(14) 6.7(12) 2.7(9) 3.8(9) -2.7(9) -0.2(9) 9.7(10) 8.6(9) 11.4(12) -5.9(12) 9.3(12) -1.0(9) -1.6(11) -21.7(14) -27.3(13) -4.1(9) 7.2(10) 21.0(11) 5.2(9) -5.9(9) 1.5(8) 9.5(14) 2.9(13) 6.1(10) -4.5(8) U13 21(8) -35(10) 2.4(7) 1.6(8) 3.1(7) 1.0(8) 0.8(9) 50(20) 1(14) -40(20) 3.9(7) 2.3(8) 1.1(8) 1.3(7) 0.0(8) -6.0(8) 10.6(8) 11.1(10) -1.4(9) -1.6(9) 4.0(8) 9.6(8) 6.0(9) 7.7(8) 9.3(9) 16.4(9) 11.9(12) 1.0(9) 24.4(14) 3.9(7) -0.6(9) -2.2(10) 16.1(12) 12.5(9) 21.5(10) 16.3(10) 8.0(8) 5.7(8) 6.3(8) 44.8(18) 0.9(10) 7.8(11) -5.3(8) U12 -7(8) 25(8) -3.9(7) -0.6(8) -0.8(7) -1.6(9) 4.4(9) 80(20) -14(13) 5(15) -2.4(8) -2.1(9) -2.6(8) -1.8(8) 0.1(8) -2.3(9) -9.7(9) -18.6(11) -16.0(13) 1.0(11) 0.8(9) 5.1(9) 2.2(9) 1.0(9) 3.3(10) -2.0(9) 17.9(12) 1.8(13) -3.2(13) 2.4(8) 6.3(10) -2.5(12) -15.9(11) -4.4(8) 1.3(9) 15.0(11) 7.2(10) -0.7(8) 3.5(8) 1.4(14) 12.1(14) 10.9(10) -4.6(8) Table 3: Bond Lengths in Å for 20231025TR_4,6,8-Trimethylazulene. Atom C1 C1 C1 C2 C2 C2 C2 C2 C2 C2 C4 C4 C5A C5A C5A C5A Atom C2 C4 C16 F3A F3B F3C F3D F3E F3F N3B C5A C7 N6A F6A F6B F6C Length/Å 1.516(3) 1.404(3) 1.396(3) 1.364(3) 1.312(3) 1.297(3) 1.311(16) 1.384(16) 1.228(16) 1.068(16) 1.449(3) 1.402(3) 1.132(3) 1.188(15) 1.444(14) 1.502(14) Atom C7 C7 C8 C10 C10 C11 C11 C11 C11 C13 C13 C14 C16 C17 C19 C19 Atom C8 C10 N9 C11 C13 N12 F12C F12B F12A C14 C16 N15 C17 N18 C20 C23 Length/Å 1.442(3) 1.393(3) 1.144(3) 1.438(3) 1.407(3) 1.130(3) 1.57(3) 1.57(3) 1.43(3) 1.437(3) 1.399(3) 1.145(3) 1.447(3) 1.140(3) 1.406(3) 1.486(3) Atom C19 C20 C21 C22 C23 C24 C24 C25 C26 C26 C27 C28 C32 Atom C28 C21 C22 C23 C24 C25 C29 C26 C27 C30 C28 C31 C33 Length/Å 1.403(3) 1.392(4) 1.385(4) 1.407(3) 1.398(3) 1.399(3) 1.503(3) 1.395(3) 1.390(3) 1.509(3) 1.400(3) 1.507(3) 1.411(3) Atom C32 C32 C33 C34 C35 C36 C37 C37 C38 C39 C39 C40 C41 Atom C36 C41 C34 C35 C36 C37 C38 C42 C39 C40 C43 C41 C44 Length/Å 1.475(3) 1.403(3) 1.383(4) 1.386(4) 1.408(3) 1.387(3) 1.398(4) 1.513(3) 1.397(3) 1.394(3) 1.507(3) 1.394(3) 1.499(3) Table 4: Bond Angles in ° for 20231025TR_4,6,8-Trimethylazulene. Atom C4 C16 C16 F3A F3B F3B F3C F3C F3C F3D F3D F3E F3F F3F F3F N3B C1 C7 C7 C4 N6A F6A F6A F6A F6B F6B C4 C10 C10 N9 C7 C7 C13 C10 C10 N12 F12C F12A F12A F12A C10 C16 C16 N15 C1 Atom C1 C1 C1 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C4 C4 C4 C5A C5A C5A C5A C5A C5A C5A C7 C7 C7 C8 C10 C10 C10 C11 C11 C11 C11 C11 C11 C11 C13 C13 C13 C14 C16 Atom C2 C2 C4 C1 C1 F3A C1 F3A F3B C1 F3E C1 C1 F3D F3E C1 C5A C1 C5A F6C C4 C4 F6B F6C C4 F6C C8 C4 C8 C7 C11 C13 C11 F12C F12B C10 F12B C10 F12C F12B C14 C10 C14 C13 C13 Angle/° 119.27(18) 121.32(17) 119.41(18) 110.75(18) 112.57(19) 104.3(2) 115.7(2) 104.5(2) 108.2(3) 116.5(7) 101.4(11) 109.2(8) 114.0(10) 110.3(12) 103.9(11) 166.0(9) 121.78(18) 120.59(18) 117.62(17) 113.3(6) 176.8(2) 127.0(8) 103.8(11) 100.5(12) 115.3(6) 89.9(10) 120.07(18) 119.89(17) 120.02(17) 179.2(2) 120.82(17) 119.62(17) 119.54(18) 126.7(12) 124.1(10) 178.2(2) 80.5(19) 129.2(11) 94.8(19) 86.4(17) 119.57(18) 120.36(18) 120.07(18) 178.7(2) 120.12(17) Atom C1 C13 N18 C20 C28 C28 C21 C22 C21 C22 C24 C24 C23 C23 C25 C26 C25 C27 C27 C26 C19 C27 C27 C33 C41 C41 C34 C33 C34 C35 C37 C37 C36 C36 C38 C39 C38 C40 C40 C39 C32 C40 C40 Atom C16 C16 C17 C19 C19 C19 C20 C21 C22 C23 C23 C23 C24 C24 C24 C25 C26 C26 C26 C27 C28 C28 C28 C32 C32 C32 C33 C34 C35 C36 C36 C36 C37 C37 C37 C38 C39 C39 C39 C40 C41 C41 C41 Atom C17 C17 C16 C23 C20 C23 C19 C20 C23 C19 C19 C22 C25 C29 C29 C24 C30 C25 C30 C28 C31 C19 C31 C36 C33 C36 C32 C35 C36 C32 C32 C35 C38 C42 C42 C37 C43 C38 C43 C41 C44 C32 C44 Angle/° 122.93(18) 116.95(18) 176.6(2) 106.0(2) 125.0(2) 129.0(2) 109.0(2) 109.7(2) 108.8(2) 106.4(2) 128.32(19) 125.2(2) 126.6(2) 117.8(2) 115.6(2) 130.6(2) 114.9(2) 128.5(2) 116.6(2) 131.0(2) 117.8(2) 125.9(2) 116.4(2) 106.62(19) 124.8(2) 128.60(18) 108.8(2) 109.3(2) 109.5(2) 105.7(2) 129.0(2) 125.3(2) 126.0(2) 117.3(2) 116.7(2) 131.5(2) 116.6(2) 127.1(2) 116.2(2) 131.4(2) 117.46(19) 126.03(19) 116.51(19) Table 5: Hydrogen Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 20231025TR_4,6,8-Trimethylazulene. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom x 9782.53 10611.48 10418.52 10430.03 9594.92 9479.02 8221.21 7477.63 7347.44 8527.37 8296.79 9351.18 4714.98 4385.25 5009.28 6635.02 6462.64 5152.35 6183.39 6021.59 6699.95 7554.9 7476.14 5698.27 5755.18 4791.62 H20 H21 H22 H29A H29B H29C H30A H30B H30C H31A H31B H31C H33 H34 H35 H38 H40 H42A H42B H42C H43A H43B H43C H44A H44B H44C y 6782.76 5727.53 4225.25 3216.72 2750.86 2998.86 4273.68 5019.13 4057.05 7264.32 7244.82 7340.14 6011.11 4533.9 3413.76 4021.83 6563.68 2883 2809.23 2779.56 5646.03 5966.35 4962.72 7085.65 7416.77 7059.28 z 7345.14 8500.98 7834.66 6496.73 5838.48 6939.63 3241.69 3402.97 3817.32 6251.26 5096.78 5572.35 7020.57 6326.19 7518.33 10564.73 10020.25 9331.98 9877.07 8717.87 11734.91 11182.09 11483.06 7872.59 8971.6 8439.73 Ueq 63 71 61 84 84 84 83 83 83 91 91 91 55 69 65 56 43 107 107 107 91 91 91 72 72 72 Table 6: Atomic Occupancies for all atoms that are not fully occupied in 20231025TR_4,6,8-Trimethylazulene. Atom F3A F3B F3C F3D Occupancy 0.707(8) 0.707(8) 0.707(8) 0.110(8) Atom F3E F3F N3B N6A Occupancy 0.110(8) 0.110(8) 0.113(3) 0.887(3) Atom F6A F6B F6C F12C Occupancy 0.113(3) 0.113(3) 0.113(3) 0.071(3) Atom F12B F12A Occupancy 0.071(3) 0.071(3) Citations O.V. Dolomanov and L.J. Bourhis and R.J. Gildea and J.A.K. Howard and H. Puschmann, Olex2: A complete structure solution, refinement and analysis program, J. Appl. Cryst., (2009), 42, 339-341. 20240129TR_COMP2_B ? (d, operator_header)Sample ID: R1=2.14% 20240129TR_COMP2_B Crystal Data and Experimental Compound Experimental. Single yellow needle-shaped crystals of 20240129TR_COMP2_B were obtained by recrystallisation from .... A suitable crystal 3 0.18×0.03×0.02 mm was selected and mounted on a suitable support on an XtaLAB Synergy R, DW system, HyPix diffractometer. The crystal was kept at a steady T = 100.00(10) K during data collection. The structure was solved with the ShelXT (Sheldrick, 2015) structure solution program using the Intrinsic Phasing solution method and by using Olex2 (Dolomanov et al., 2009) as the graphical interface. The model was refined with version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015) using Least Squares minimisation. Crystal Data. C32H27F4N3O2Pt, Mr = 756.65, orthorhombic, Pnma (No. 62), a = 25.9929(3) Å, b = 6.78700(10) Å, c = 16.1287(2) Å,  =  =  = 90°, V = 2845.33(6) Å3, T = 100.00(10) K, Z = 4, Z' = 0.5, (Cu K) = 9.758, 29314 reflections measured, 2945 unique (Rint = 0.0483) which were used in all calculations. The final wR2 was 0.0517 (all data) and R1 was 0.0214 (I > 2(I)). 20240129TR_COM P2_B Formula C32H27F4N3O2Pt Dcalc./ g cm-3 1.766 -1 9.758 /mm Formula Weight 756.65 Colour yellow Shape needle Size/mm3 0.18×0.03×0.02 T/K 100.00(10) Crystal System orthorhombic Space Group Pnma a/Å 25.9929(3) b/Å 6.78700(10) c/Å 16.1287(2) 90 /° ° 90 / ° 90 / V/Å3 2845.33(6) Z 4 Z' 0.5 Wavelength/Å 1.54184 Radiation type Cu K 3.225 min/° ° 70.064 max/ Measured Refl. 29314 Independent Refl. 2945 Reflections with I > 2796 2(I) Rint 0.0483 Parameters 249 Restraints 0 Largest Peak 0.679 Deepest Hole -0.645 GooF 1.084 wR2 (all data) 0.0517 wR2 0.0507 R1 (all data) 0.0237 R1 0.0214 Structure Quality Indicators Reflections: Refinement: Experimental Extended. A yellow needle-shaped crystal with dimensions 0.18×0.03×0.02 mm3 was mounted on a suitable support. Data were collected using an XtaLAB Synergy R, DW system, HyPix diffractometer operating at T = 100.00(10) K. Data were measured using  scans of 0.5° per frame for 0.2/0.9 s using Cu K radiation. The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) The maximum resolution that was achieved was  = 70.064° (0.82 Å). The diffraction pattern was indexed The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) and the unit cell was refined using CrysAlisPro (Rigaku, V1.171.42.93a, 2023) on 16321 reflections, 56% of the observed reflections. Data reduction, scaling and absorption corrections were performed using CrysAlisPro (Rigaku, V1.171.42.93a, 2023). The final completeness is 99.90 % out to 70.064° in . A gaussian absorption correction was performed using CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. The absorption coefficient  of this material is 9.758 mm-1 at this wavelength ( = 1.542Å) and the minimum and maximum transmissions are 0.082 and 0.795. The structure was solved and the space group Pnma (# 62) determined by the ShelXT (Sheldrick, 2015) structure solution program using Intrinsic Phasing and refined by Least Squares using version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model. Hydrogen atom positions were calculated geometrically and refined using the riding model. _exptl_absorpt_process_details: CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. Table 1: Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å 2×103) for 20240129TR_COMP2_B. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom Pt1 N2 C3 C4 C5 C7 C8 C9 C10 C11 C12 C13 x 8481.7(2) 8485.6(12) 8082.6(16) 8140.6(16) 8632.6(18) 8976.7(16) 9385.5(15) 9238.5(15) 9633.5(14) 10151.4(16) 10280.8(15) 9895.1(16) y 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 z 3302.2(2) 2057(2) 1543(2) 681(2) 347(2) 1724(2) 2308(2) 3150(2) 3729(2) 3471(3) 2647(3) 2032(3) Ueq 14.92(7) 19.7(7) 21.1(8) 24.9(8) 26.1(9) 19.0(8) 20.5(8) 17.5(7) 20.1(8) 24.8(8) 26.0(9) 24.4(8) Atom C14 C15 C16 O17 O18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 N30 C31 F32 C33 F34 C35 C36 N37 C38 F39 C40 F41 x 9984.6(17) 9592.9(18) 9062.6(17) 7690.7(10) 8549.3(10) 7648.1(14) 8164.8(15) 8334.0(14) 7886.9(15) 8667.5(12) 7434.0(14) 6850.1(15) 6540.3(15) 6719.0(11) 6254.7(17) 6738.0(18) 7122.0(16) 6234.4(15) 6672.4(10) 5775.5(16) 5764.0(10) 5310.4(15) 4830.7(16) 4447.2(16) 5330.2(16) 4895.7(9) 5794.4(16) 5801.3(11) y 7500 7500 7500 7500 7500 7500 7500 7500 7500 9346(4) 7500 7500 7500 5651(5) 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 z 1153(3) 598(3) 869(2) 3349.6(15) 4535.6(17) 4822(2) 5039(2) 5948(2) 6565(2) 6089.5(17) 4028(2) 3895(2) 4703(2) 3393.2(17) 8346(3) 8784(3) 9142(3) 7485(3) 7048.5(18) 7079(2) 6250.2(15) 7511(2) 7078(3) 6717(2) 8374(2) 8811.7(15) 8782(2) 9608.9(15) Ueq 30.2(9) 29.3(9) 25.1(8) 19.0(5) 20.5(6) 17.6(7) 18.1(7) 18.1(7) 22.8(8) 26.7(6) 17.3(7) 19.6(8) 22.9(8) 27.7(6) 25.3(9) 32.9(10) 44.3(11) 23.8(8) 34.8(6) 23.1(8) 32.5(6) 20.4(8) 26.0(9) 36.2(9) 22.8(8) 30.3(5) 23.0(8) 35.6(6) Table 2: Anisotropic Displacement Parameters (×104) 20240129TR_COMP2_B. The anisotropic displacement factor exponent takes the form: -22[h2a*2 × U11+ ... +2hka* × b* × U12] Atom Pt1 N2 C3 C4 C5 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 O17 O18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 N30 U11 16.05(10) 22.1(17) 25(2) 32(2) 42(2) 29(2) 26(2) 22.1(19) 16.2(19) 22(2) 15.8(19) 25(2) 27(2) 37(2) 37(2) 17.6(13) 17.8(13) 16.4(17) 26.4(19) 17.8(18) 24(2) 31.0(15) 17.0(18) 20.2(19) 21(2) 25.6(15) 25(2) 30(2) 36(2) U22 13.89(9) 14.8(15) 16.7(17) 21.8(19) 19.8(19) 7.3(15) 12.5(16) 12.8(16) 18.7(17) 20.6(19) 26(2) 17.3(18) 31(2) 29(2) 17.5(18) 22.8(13) 24.2(14) 18.0(17) 9.9(15) 20.0(18) 27(2) 27.0(15) 13.1(16) 20.3(18) 25(2) 29.9(16) 17.7(19) 20(2) 24.6(19) U33 14.81(9) 22.3(17) 22.0(18) 21.2(18) 16.3(18) 20.5(18) 23.4(19) 17.7(17) 25.4(19) 32(2) 36(2) 31(2) 33(2) 22.6(19) 20.8(18) 16.7(12) 19.5(13) 18.5(17) 18.0(17) 16.7(17) 17.3(17) 22.1(13) 21.6(18) 18.3(17) 23.3(19) 27.7(14) 33(2) 48(3) 72(3) U23 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 -4.3(11) 0 0 0 -5.3(12) 0 0 0 U13 -0.03(6) 0.6(13) -1.8(16) -5.3(17) -4.8(17) 4.3(15) 0.1(16) 3.4(15) -2.1(15) -4.1(17) 5.5(16) 7.2(17) 10.8(18) 10.9(19) 1.9(17) 0.2(10) 0.4(10) 3.2(14) 2.7(16) -2.7(14) -1.6(16) -1.8(11) 2.6(14) -2.2(15) 1.5(15) -2.0(11) -5.7(17) -6(2) -20(2) U12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 -7.7(12) 0 0 0 -4.7(13) 0 0 0 Atom C31 F32 C33 F34 C35 C36 N37 C38 F39 C40 F41 U11 20(2) 25.1(13) 30(2) 41.0(15) 20.7(19) 29(2) 32(2) 25(2) 24.5(12) 30(2) 46.3(15) U22 15.2(17) 31.2(13) 18.1(18) 33.8(13) 14.0(17) 19.9(19) 34(2) 18.5(18) 33.8(13) 13.8(17) 38.4(14) U33 36(2) 48.1(15) 21.6(19) 22.6(12) 26.5(19) 29(2) 42(2) 24.8(19) 32.7(12) 25.2(19) 22.2(12) U23 U13 9.1(17) 13.1(12) 4.5(16) 6.2(11) 0.9(15) 2.1(18) -8.3(17) 7.1(16) 10.6(10) -4.1(17) -5.5(11) 0 0 0 0 0 0 0 0 0 0 0 U12 0 0 0 0 0 0 0 0 0 0 0 Table 3: Bond Lengths in Å for 20240129TR_COMP2_B. Atom Pt1 Pt1 Pt1 Pt1 N2 N2 C3 C4 C5 C7 C7 C8 C8 C9 C10 C11 C12 C13 C14 C15 O17 O18 C19 C19 Atom N2 C9 O17 O18 C3 C7 C4 C5 C16 C8 C16 C9 C13 C10 C11 C12 C13 C14 C15 C16 C24 C20 C20 C24 Length/Å 2.009(3) 1.982(4) 2.058(3) 1.997(3) 1.335(5) 1.385(5) 1.398(6) 1.388(6) 1.399(6) 1.420(6) 1.398(5) 1.410(5) 1.398(6) 1.388(5) 1.409(6) 1.371(6) 1.411(6) 1.436(6) 1.356(7) 1.446(6) 1.281(4) 1.288(5) 1.388(5) 1.397(5) Atom Atom C20 C21 C21 C22 C21 C23 C21 C231 C24 C25 C25 C26 C25 C271 C25 C27 C28 C29 C28 C31 C28 C40 C29 N30 C31 F32 C31 C33 C33 F34 C33 C35 C35 C36 C35 C38 C36 N37 C38 F39 C38 C40 C40 F41 –––– 1+x,3/2-y,+z Length/Å 1.531(5) 1.529(5) 1.540(3) 1.540(3) 1.533(5) 1.532(5) 1.531(3) 1.531(3) 1.441(6) 1.389(6) 1.388(6) 1.153(6) 1.339(5) 1.361(6) 1.337(5) 1.395(6) 1.429(6) 1.393(5) 1.155(6) 1.332(5) 1.374(6) 1.333(5) Table 4: Bond Angles in ° for 20240129TR_COMP2_B. Atom N2 C9 C9 C9 O18 O18 C3 C3 C7 N2 C5 C4 N2 N2 C16 C9 C13 C13 Atom Pt1 Pt1 Pt1 Pt1 Pt1 Pt1 N2 N2 N2 C3 C4 C5 C7 C7 C7 C8 C8 C8 Atom O17 N2 O17 O18 N2 O17 Pt1 C7 Pt1 C4 C3 C16 C8 C16 C8 C7 C7 C9 Angle/° 92.41(11) 82.59(14) 175.00(12) 92.08(13) 174.67(11) 92.92(10) 128.1(3) 118.9(3) 113.0(2) 122.2(4) 119.0(4) 120.2(4) 115.7(3) 121.9(4) 122.4(4) 115.8(3) 119.8(4) 124.3(4) Atom C8 C10 C10 C9 C12 C11 C8 C8 C12 C15 C14 C5 C7 C7 C24 C20 C20 O18 Atom C9 C9 C9 C10 C11 C12 C13 C13 C13 C14 C15 C16 C16 C16 O17 O18 C19 C20 Atom Pt1 Pt1 C8 C11 C10 C13 C12 C14 C14 C13 C16 C15 C5 C15 Pt1 Pt1 C24 C19 Angle/° 112.9(3) 130.6(3) 116.6(4) 120.5(4) 121.4(4) 120.5(4) 116.7(4) 117.9(4) 125.4(4) 122.0(4) 121.1(4) 125.4(4) 117.8(4) 116.8(4) 123.5(2) 124.0(2) 128.1(3) 126.3(3) Atom O18 C19 C20 C20 C22 C22 C22 C23 O17 O17 C19 C26 C271 C27 C27 C271 C27 C31 C40 C40 Atom C20 C20 C21 C21 C21 C21 C21 C21 C24 C24 C24 C25 C25 C25 C25 C25 C25 C28 C28 C28 Atom C21 C21 C23 C231 C20 C231 C23 C231 C19 C25 C25 C24 C24 C24 C26 C26 C271 C29 C29 C31 Angle/° 112.4(3) 121.3(3) 107.7(2) 107.7(2) 113.8(3) 109.4(2) 109.4(2) 108.8(3) 125.1(3) 113.3(3) 121.5(3) 113.7(3) 107.1(2) 107.1(2) 109.4(2) 109.4(2) 110.1(3) 121.5(4) 120.2(4) 118.3(4) Atom Atom N30 C29 F32 C31 F32 C31 C33 C31 C31 C33 F34 C33 F34 C33 C33 C35 C38 C35 C38 C35 N37 C36 F39 C38 F39 C38 C40 C38 C38 C40 F41 C40 F41 C40 –––– 1+x,3/2-y,+z Atom C28 C28 C33 C28 C35 C31 C35 C36 C33 C36 C35 C35 C40 C35 C28 C28 C38 Angle/° 179.3(6) 119.6(4) 119.5(4) 121.0(4) 121.3(4) 120.1(4) 118.7(4) 120.8(4) 117.8(4) 121.4(4) 178.9(4) 119.9(4) 119.4(4) 120.7(4) 120.9(4) 119.7(4) 119.4(4) Table 5: Hydrogen Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 20240129TR_COMP2_B. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom x 7745.54 7847.48 8677.58 9554.04 10416.45 10632.95 10328.79 9668.11 7410.44 8022.52 7675.91 7675.91 8955.69 8800.55 8458.32 6623.99 6171.87 6627.06 6888.86 6345.68 6838.49 H3 H4 H5 H10 H11 H12 H14 H15 H19 H22A H22B H22C H23A H23B H23C H26A H26B H26C H27A H27B H27C y 7500 7500 7500 7500 7500 7500 7500 7500 7500 7500 8678.97 6321.03 9343.15 9339.57 10529.33 8682.94 7492.01 6325.04 5716.36 5572.01 4480.78 z 1770.46 329.12 -237.58 4303.83 3876.49 2489.35 955.05 21.42 5269.73 7131.76 6478.81 6478.81 5697.79 6658 6002.51 5024.11 4574.14 5027.16 2851.43 3314.6 3692.61 Ueq 25 30 31 24 30 31 36 35 21 34 34 34 40 40 40 34 34 34 42 42 42 Table 6: Atomic Occupancies for all atoms that are not fully occupied in 20240129TR_COMP2_B. Atom H22A H22B H22C Occupancy 0.5 0.5 0.5 Atom H26A H26B H26C Occupancy 0.5 0.5 0.5 Citations O.V. Dolomanov and L.J. Bourhis and R.J. Gildea and J.A.K. Howard and H. Puschmann, Olex2: A complete structure solution, refinement and analysis program, J. Appl. Cryst., (2009), 42, 339-341. 20240228TR_AE-TMA ? (d, operator_header)Sample ID: R1=3.30% 20240228TR_AE-TMA Crystal Data and Experimental Compound Experimental. Single dark orange plate-shaped crystals of 20240228TR_AE-TMA were obtained by recrystallisation from .... A suitable crystal 3 0.19×0.08×0.04 mm was selected and mounted on a suitable support on an XtaLAB Synergy R, DW system, HyPix diffractometer. The crystal was kept at a steady T = 99.99(10) K during data collection. The structure was solved with the ShelXT 2018/2 (Sheldrick, 2018) structure solution program using the Intrinsic Phasing solution method and by using Olex2 (Dolomanov et al., 2009) as the graphical interface. The model was refined with version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015) using Least Squares minimisation. Crystal Data. C21H14F4N2, Mr = 370.34, monoclinic, P2/n (No. 13), a = 6.70520(10) Å, b = 14.5032(2) Å, c = 9.2614(2) Å,  = 109.891(2)°,  =  = 90°, V = 846.91(3) Å3, T = 99.99(10) K, Z = 2, Z' = 0.5, (Cu K) = 1.000, 16622 reflections measured, 1742 unique (Rint = 0.0273) which were used in all calculations. The final wR2 was 0.0911 (all data) and R1 was 0.0330 (I > 2(I)). 20240228TR_AE-T MA Formula C21H14F4N2 Dcalc./ g cm-3 1.452 -1 1.000 /mm Formula Weight 370.34 Colour dark orange Shape plate Size/mm3 0.19×0.08×0.04 T/K 99.99(10) Crystal System monoclinic Space Group P2/n a/Å 6.70520(10) b/Å 14.5032(2) c/Å 9.2614(2) 90 /° ° 109.891(2) / ° 90 / V/Å3 846.91(3) Z 2 Z' 0.5 Wavelength/Å 1.54184 Radiation type Cu K 3.047 min/° ° 74.449 max/ Measured Refl. 16622 Independent Refl. 1742 Reflections with I > 1593 2(I) Rint 0.0273 Parameters 129 Restraints 0 Largest Peak 0.173 Deepest Hole -0.258 GooF 1.073 wR2 (all data) 0.0911 wR2 0.0888 R1 (all data) 0.0355 R1 0.0330 Structure Quality Indicators Reflections: Refinement: Experimental Extended. A dark orange plate-shaped crystal with dimensions 0.19×0.08×0.04 mm3 was mounted on a suitable support. Data were collected using an XtaLAB Synergy R, DW system, HyPix diffractometer operating at T = 99.99(10) K. Data were measured using  scans of 0.5° per frame for 0.1 s using Cu K radiation. The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) The maximum resolution that was achieved was  = 74.449° (0.80 Å). The diffraction pattern was indexed The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku, V1.171.42.93a, 2023) and the unit cell was refined using CrysAlisPro (Rigaku, V1.171.42.93a, 2023) on 11145 reflections, 67% of the observed reflections. Data reduction, scaling and absorption corrections were performed using CrysAlisPro (Rigaku, V1.171.42.93a, 2023). The final completeness is 100.00 % out to 74.449° in . A gaussian absorption correction was performed using CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. The absorption coefficient  of this material is 1.000 mm-1 at this wavelength ( = 1.542Å) and the minimum and maximum transmissions are 0.668 and 1.000. The structure was solved and the space group P2/n (# 13) determined by the ShelXT 2018/2 (Sheldrick, 2018) structure solution program using Intrinsic Phasing and refined by Least Squares using version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model. Hydrogen atom positions were calculated geometrically and refined using the riding model. _exptl_absorpt_process_details: CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. Table 1: Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å 2×103) for 20240228TR_AE-TMA. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom F3 F2 N8 N6 C11 C4 C7 C12 C3 C2 C15 C14 x 8492.3(10) 8521.5(11) 7500 7500 2148.6(15) 7500 7500 1774.4(16) 8004.6(15) 8013.6(16) 2500 1977.9(15) y 6366.0(5) 8222.3(5) 4549.3(9) 10037.0(10) 6988.2(7) 6327.1(10) 5339.6(10) 7744.6(7) 6817.8(7) 7767.2(7) 9098.0(10) 8675.0(7) z 10194.7(7) 10195.2(7) 7500 7500 6645.6(11) 7500 7500 5641.7(12) 8869.2(11) 8866.5(12) 7500 6063.2(12) Ueq 30.3(2) 32.5(2) 29.5(3) 40.3(4) 19.4(2) 20.1(3) 23.1(3) 20.4(2) 21.5(2) 22.5(3) 21.0(3) 21.8(2) Atom C1 C10 C9 C5 C16 C13 x 7500 1955.2(16) 2500 7500 2500 1073.9(19) y 8257.7(10) 6057.3(8) 5502.3(11) 9247.5(11) 10141.2(10) 7546.4(8) z 7500 6187.8(12) 7500 7500 7500 3940.7(13) Ueq 22.2(3) 23.3(2) 25.1(3) 28.7(4) 25.9(3) 28.6(3) Table 2: Anisotropic Displacement Parameters (×104) 20240228TR_AE-TMA. The anisotropic displacement factor exponent takes the form: -22[h2a*2 × U11+ ... +2hka* × b* × U12] Atom F3 F2 N8 N6 C11 C4 C7 C12 C3 C2 C15 C14 C1 C10 C9 C5 C16 C13 U11 35.9(4) 36.1(4) 31.3(7) 33.1(8) 16.1(5) 17.0(6) 20.2(7) 17.2(5) 19.3(5) 19.3(5) 15.5(6) 19.3(5) 16.8(6) 22.2(5) 24.3(7) 21.6(7) 24.0(7) 34.7(6) U22 33.2(4) 33.3(4) 23.1(7) 22.8(7) 21.9(5) 20.1(7) 24.1(8) 25.7(5) 25.1(6) 24.8(6) 20.4(7) 24.0(5) 20.3(7) 23.6(5) 19.4(7) 24.1(8) 19.5(7) 32.0(6) U33 21.3(3) 28.2(4) 36.3(8) 72.2(12) 22.1(6) 24.5(7) 26.5(8) 19.6(5) 21.0(5) 24.7(6) 28.4(8) 23.3(5) 31.8(8) 26.5(6) 35.4(8) 45.0(9) 34.5(8) 19.5(6) U23 5.9(3) -12.2(3) 0 0 -1.2(4) 0 0 -0.1(4) 2.6(4) -6.4(4) 0 4.4(4) 0 -4.2(4) 0 0 0 0.2(4) U13 9.0(3) 10.9(3) 14.2(6) 27.3(8) 9.0(4) 8.9(6) 9.9(6) 7.9(4) 8.0(4) 9.0(4) 9.1(6) 8.9(4) 11.1(6) 11.4(4) 15.1(6) 17.2(7) 10.2(6) 9.8(5) U12 2.8(3) -2.7(3) 0 0 0.4(4) 0 0 1.4(4) 1.6(4) -1.4(4) 0 2.4(4) 0 -0.9(4) 0 0 0 3.8(5) Table 3: Bond Lengths in Å for 20240228TR_AE-TMA. Atom F3 F2 N8 N6 C11 C11 C11 C4 C4 C4 C12 Atom C3 C2 C7 C5 C111 C12 C10 C7 C3 C32 C14 Length/Å 1.3304(12) 1.3345(12) 1.146(2) 1.145(2) 1.490(2) 1.4042(15) 1.4079(15) 1.432(2) 1.3917(13) 1.3917(13) 1.3985(15) Atom Atom Length/Å C12 C13 1.5105(15) C3 C2 1.3769(16) C2 C1 1.3891(13) C15 C14 1.3973(12) C15 C141 1.3973(12) C15 C16 1.513(2) C1 C5 1.436(2) C10 C9 1.3986(14) –––– 11/2-x,+y,3/2-z; 23/2-x,+y,3/2-z Table 4: Bond Angles in ° for 20240228TR_AE-TMA. Atom C12 C12 C10 C32 C3 C32 N8 C11 C14 C14 F3 F3 Atom C11 C11 C11 C4 C4 C4 C7 C12 C12 C12 C3 C3 Atom C111 C10 C111 C7 C7 C3 C4 C13 C11 C13 C4 C2 Angle/° 128.61(6) 124.91(10) 106.46(6) 120.75(7) 120.75(7) 118.49(14) 180.0 117.65(9) 126.19(10) 116.16(9) 119.74(10) 119.62(9) Atom C2 F2 F2 C3 C141 C141 C14 C15 C2 C2 C22 C9 Atom C3 C2 C2 C2 C15 C15 C15 C14 C1 C1 C1 C10 Atom C4 C3 C1 C1 C14 C16 C16 C12 C22 C5 C5 C11 Angle/° 120.63(10) 119.53(9) 119.55(10) 120.92(10) 127.92(14) 116.04(7) 116.04(7) 131.18(10) 118.39(14) 120.80(7) 120.81(7) 108.67(10) Atom C101 N6 Atom C9 C5 Atom C10 C1 –––– 11/2-x,+y,3/2-z; 23/2-x,+y,3/2-z Angle/° 109.73(14) 180.0 Table 5: Hydrogen Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 20240228TR_AE-TMA. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom x 1715.59 1525.85 2499.98 3788.61 2459.95 1251.44 2017.99 1131.21 -382.09 H14 H10 H9 H16A H16B H16C H13A H13B H13C y 9091.84 5841.84 4847.3 10366.44 10366.44 10366.44 7085.33 8115.41 7309.97 z 5227.76 5158.51 7499.99 7342.4 8487.4 6670.2 3742.89 3385.35 3590.11 Ueq 26 28 30 39 39 39 43 43 43 Table 6: Atomic Occupancies for all atoms that are not fully occupied in 20240228TR_AE-TMA. Atom H16A H16B Occupancy 0.5 0.5 Atom H16C Occupancy 0.5 Citations O.V. Dolomanov and L.J. Bourhis and R.J. Gildea and J.A.K. Howard and H. Puschmann, Olex2: A complete structure solution, refinement and analysis program, J. Appl. Cryst., (2009), 42, 339-341. 20240409TR_GA_CN5 ? (d, operator_header)Sample ID: R1=5.05% 20240409TR_GA_CN5 Crystal Data and Experimental Compound Experimental. Single violet irregular-shaped crystals of 20240409TR_GA_CN5 were obtained by recrystallisation from .... A suitable crystal 3 0.12×0.04×0.03 mm was selected and mounted on a suitable support on an XtaLAB Synergy R, DW system, HyPix diffractometer. The crystal was kept at a steady T = 100.00(10) K during data collection. The structure was solved with the ShelXT (Sheldrick, 2015) structure solution program using the Intrinsic Phasing solution method and by using Olex2 (Dolomanov et al., 2009) as the graphical interface. The model was refined with version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015) using Least Squares minimisation. Crystal Data. C27H18F3N5, Mr = 469.46, triclinic, P-1 (No. 2), a = 7.1737(2) Å, b = 9.3193(2) Å, c = 17.2574(3) Å,  = 98.051(2)°,  = 93.227(2)°,  = 102.588(2)°, V = 1110.38(4) Å3, T = 100.00(10) K, Z = 2, Z' = 1, (Cu K) = 0.864, 42306 reflections measured, 4461 unique (Rint = 0.0588) which were used in all calculations. The final wR2 was 0.1396 (all data) and R1 was 0.0505 (I > 2(I)). 20240409TR_GA_C N5 Formula C27H18F3N5 Dcalc./ g cm-3 1.404 -1 0.864 /mm Formula Weight 469.46 Colour violet Shape irregular Size/mm3 0.12×0.04×0.03 T/K 100.00(10) Crystal System triclinic Space Group P-1 a/Å 7.1737(2) b/Å 9.3193(2) c/Å 17.2574(3) 98.051(2) /° ° 93.227(2) / ° 102.588(2) / V/Å3 1110.38(4) Z 2 Z' 1 Wavelength/Å 1.54184 Radiation type Cu K 2.596 min/° ° 74.486 max/ Measured Refl. 42306 Independent Refl. 4461 Reflections with I > 3508 2(I) Rint 0.0588 Parameters 348 Restraints 114 Largest Peak 0.481 Deepest Hole -0.261 GooF 1.046 wR2 (all data) 0.1396 wR2 0.1289 R1 (all data) 0.0674 R1 0.0505 Structure Quality Indicators Reflections: Refinement: Experimental Extended. A violet irregular-shaped crystal with dimensions 0.12×0.04×0.03 mm3 was mounted on a suitable support. Data were collected using an XtaLAB Synergy R, DW system, HyPix diffractometer operating at T = 100.00(10) K. Data were measured using  scans of 0.5° per frame for 0.1 s using Cu K radiation. The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku) The maximum resolution that was achieved was  = 74.486° (0.80 Å). The diffraction pattern was indexed The diffraction pattern was indexed and the total number of runs and images was based on the strategy calculation from the program CrysAlisPro (Rigaku) and the unit cell was refined using CrysAlisPro (Rigaku, V1.171.43.90, 2023) on 17411 reflections, 41% of the observed reflections. Data reduction, scaling and absorption corrections were performed using CrysAlisPro (Rigaku, V1.171.43.90, 2023). The final completeness is 100.00 % out to 74.486 ° in . A gaussian absorption correction was performed using CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. The absorption coefficient  of this material is 0.864 mm-1 at this wavelength ( = 1.542Å) and the minimum and maximum transmissions are 0.844 and 1.000. The structure was solved and the space group P-1 (# 2) determined by the ShelXT (Sheldrick, 2015) structure solution program using Intrinsic Phasing and refined by Least Squares using version 2018/3 of ShelXL 2018/3 (Sheldrick, 2015). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model. Hydrogen atom positions were calculated geometrically and refined using the riding model. _exptl_absorpt_process_details: CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)Numerical absorption correction based on gaussian integration overa multifaceted crystal modelEmpirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm. Table 1: Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å 2×103) for 20240409TR_GA_CN5. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom C1 N1 C2 F3 F4 F5 C6 C7 C8 C9 N10 C11 x 4089(2) 2045(2) 3591(3) 3916(7) 4659(4) 1804(3) 3704(2) 2755(2) 4275(2) 3927(2) 3710(2) 5278(2) y 1625(2) 1720(2) -33(2) -860(2) -295(3) -502(3) 2611(2) 2091(2) 4160(2) 5183(2) 6033.8(19) 4713(2) z 6640.2(11) 4737.7(10) 6331.6(12) 6856.4(19) 5739(2) 6039(2) 6147.4(10) 5363.9(11) 6394.8(10) 5886.6(10) 5487.6(9) 7134.7(10) Ueq 23.3(4) 32.1(4) 30.0(4) 61.0(14) 53.0(10) 36.2(7) 22.0(4) 24.2(4) 21.3(4) 22.9(4) 28.0(4) 21.6(4) Atom C12 N13 C14 C15 N16 C17 C18 N19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 F4A F3A F5A x 5965(3) 6571(3) 5647(2) 6661(3) 7465(2) 5035(2) 5401(3) 5700(3) -554(3) -394(3) -1112(3) -781(3) 171(3) 427(3) 1314(3) 2178(3) 2311(3) 1710(3) 748(3) 2920(3) 4805(3) 1384(3) 314(3) 5078(10) 2680(30) 2350(30) y 6291(2) 7536.3(19) 3731(2) 4297(2) 4745.4(19) 2184(2) 1271(2) 655(2) 5728(2) 4397(2) 2907(2) 1939(2) 2781(2) 4367(2) 5643(2) 5792(2) 4606(2) 3076(2) 2205(2) 7382(2) 7622(2) 7832(3) 554(2) -535(9) -742(10) -481(13) z 7377.7(11) 7565.9(11) 7629.4(10) 8392.6(11) 9001.6(9) 7392.2(11) 7963.0(11) 8473.0(10) 6154.4(12) 6521.5(11) 6163.6(12) 6671.9(11) 7382.8(12) 7280.2(11) 7809.7(11) 8570.6(11) 8966.4(11) 8741.9(12) 8040.1(12) 9004.2(12) 9517.2(12) 9499.2(14) 8031.2(14) 6229(12) 6898(6) 5708(9) Ueq 24.4(4) 35.8(4) 21.6(4) 23.8(4) 30.7(4) 22.6(4) 26.2(4) 33.6(4) 32.2(5) 28.2(4) 31.4(5) 27.6(4) 27.6(4) 26.5(4) 26.5(4) 24.3(4) 29.2(4) 29.4(4) 28.2(4) 30.6(4) 31.1(4) 39.4(5) 37.3(5) 57(5) 61(5) 65(5) Table 2: Anisotropic Displacement Parameters (×104) 20240409TR_GA_CN5. The anisotropic displacement factor exponent takes the form: -22[h2a*2 × U11+ ... +2hka* × b* × U12] Atom C1 N1 C2 F3 F4 F5 C6 C7 C8 C9 N10 C11 C12 N13 C14 C15 N16 C17 C18 N19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 U11 19.5(8) 28.5(8) 28.7(10) 99(3) 43.7(13) 26.9(9) 17.3(8) 20.5(8) 17.3(8) 20.2(8) 27.1(8) 18.4(8) 24.4(9) 39.4(10) 16.7(8) 20.8(8) 29.7(8) 18.5(8) 23.0(9) 36.6(9) 27.9(10) 20.7(9) 22.9(9) 20.3(9) 20.0(9) 19.1(8) 24.3(9) 21.9(9) 28.5(10) 27.6(10) 22.4(9) U22 20.7(9) 35.0(10) 24.1(10) 20.5(9) 31.0(10) 21.2(8) 24.0(9) 23.0(9) 23.8(9) 24.0(9) 28.2(9) 21.6(9) 24.1(10) 24.9(10) 23.3(9) 23.2(9) 31.8(9) 22.6(9) 23.2(10) 29.2(9) 40.6(12) 34.7(11) 40.3(12) 26.2(10) 26.4(10) 31.0(11) 27.6(10) 24.6(10) 31.5(11) 29.9(11) 28.8(10) U33 27.7(9) 28.5(9) 34.2(10) 56.1(15) 77(2) 53.1(16) 22.6(9) 27.8(10) 22.2(9) 22.7(9) 28.9(8) 23.4(9) 23.2(9) 38.5(10) 23.4(9) 26.8(10) 27.0(9) 26.0(9) 30.4(10) 35.2(9) 28.6(10) 29.5(10) 27.7(10) 32.1(10) 34.6(10) 29.4(10) 28.1(10) 24.3(9) 25.7(9) 31.1(10) 33.5(10) U23 -0.2(7) -2.7(7) -0.7(8) -0.7(8) -18.4(11) -5.1(10) -1.9(7) -0.7(7) 0.8(7) -2.3(7) 4.7(7) 0.3(7) 0.9(7) -1.0(7) -0.3(7) 3.3(7) 0.9(7) 2.7(7) -0.4(8) 5.3(8) 7.8(9) 3.6(8) -4.7(8) -5.2(8) 0.2(8) 3.0(8) 4.9(8) 1.0(7) 2.6(8) 7.4(8) 3.8(8) U13 -1.6(7) -4.5(7) -8.1(8) -43.1(18) 15.6(13) -11.1(8) -1.8(7) -1.4(7) 0.8(6) -0.2(7) 0.6(6) 0.9(7) -1.2(7) 0.2(8) -0.1(7) 0.8(7) -3.6(7) -1.1(7) -2.9(7) -1.9(7) -2.6(8) 3.5(7) -3.0(7) -1.6(7) 1.9(7) 2.3(7) 2.0(7) 0.0(7) -0.9(8) -0.9(8) 3.1(8) U12 4.2(7) 4.5(7) 5.8(8) 15.0(12) 6.5(9) 0.0(6) 4.6(7) 5.8(7) 5.6(7) 5.4(7) 7.0(7) 4.2(7) 4.8(7) 2.2(7) 4.7(7) 4.4(7) 3.6(7) 5.1(7) 4.8(7) 9.3(7) 8.2(9) 7.5(8) 7.7(8) 3.2(7) 4.3(7) 6.9(7) 6.5(7) 3.5(7) 4.7(8) 6.7(8) 6.9(7) Atom C31 C32 C33 C34 F4A F3A F5A U11 33.4(10) 30.2(10) 35.2(11) 30.6(10) 28(4) 110(11) 91(10) U22 25.7(10) 28.4(10) 30.2(11) 27.7(11) 22(4) 17(4) 33(4) U33 29.2(10) 29.6(10) 46.5(13) 52.1(13) 113(14) 51(5) 59(7) U23 1.2(8) -2.1(8) -9.6(9) 5.8(9) -15(5) 6(3) -7(5) U13 -3.3(8) -5.3(8) -1.4(9) -4.5(9) -1(4) 30(6) -40(7) U12 3.0(8) 1.7(8) 5.4(9) 5.6(8) 7(3) -2(5) 9(6) Table 3: Bond Lengths in Å for 20240409TR_GA_CN5. Atom C1 C1 C1 N1 C2 C2 C2 C2 C2 C2 C6 C6 C8 C8 C9 C11 C11 C12 C14 C14 Atom C2 C6 C17 C7 F3 F4 F5 F4A F3A F5A C7 C8 C9 C11 N10 C12 C14 N13 C15 C17 Length/Å 1.519(3) 1.395(3) 1.405(2) 1.142(2) 1.311(3) 1.339(3) 1.308(3) 1.266(7) 1.372(7) 1.314(8) 1.448(2) 1.409(3) 1.433(3) 1.402(2) 1.149(3) 1.439(3) 1.391(3) 1.140(3) 1.440(2) 1.406(3) Atom C15 C17 C18 C20 C21 C21 C22 C23 C24 C24 C25 C26 C27 C27 C28 C29 C30 C31 C31 Atom N16 C18 N19 C21 C22 C25 C23 C24 C25 C30 C26 C27 C28 C31 C29 C30 C34 C32 C33 Atom N13 C11 C11 C17 N16 C1 C1 C14 N19 C22 C22 C25 C23 C22 C23 C30 C30 C21 C26 C26 C27 C26 C28 C28 C29 C28 Atom C12 C14 C14 C14 C15 C17 C17 C17 C18 C21 C21 C21 C22 C23 C24 C24 C24 C25 C25 C25 C26 C27 C27 C27 C28 C29 Length/Å 1.147(2) 1.438(3) 1.150(3) 1.493(3) 1.410(3) 1.412(3) 1.389(3) 1.411(3) 1.485(3) 1.401(3) 1.398(3) 1.395(3) 1.395(3) 1.530(3) 1.389(3) 1.410(3) 1.500(3) 1.530(3) 1.525(3) Table 4: Bond Angles in ° for 20240409TR_GA_CN5. Atom C6 C6 C17 F3 F3 F4 F5 F5 F5 F4A F4A F4A F3A F5A F5A C1 C1 C8 N1 C6 C11 C11 N10 C8 C14 C14 Atom C1 C1 C1 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C6 C6 C6 C7 C8 C8 C8 C9 C11 C11 C11 Atom C2 C17 C2 C1 F4 C1 C1 F3 F4 C1 F3A F5A C1 C1 F3A C7 C8 C7 C6 C9 C6 C9 C8 C12 C8 C12 Angle/° 119.10(16) 119.63(16) 121.15(17) 113.90(17) 107.4(2) 108.62(18) 112.07(18) 108.4(2) 106.10(19) 111.8(4) 106.5(6) 110.4(7) 107.5(4) 116.5(5) 103.3(7) 121.73(16) 120.53(16) 117.72(17) 177.7(2) 121.00(16) 119.59(17) 119.34(16) 177.65(19) 120.22(17) 119.90(17) 119.86(16) Atom C11 C15 C17 C15 C14 C14 C18 C18 C17 C20 C25 C20 C21 C24 C25 C23 C25 C24 C21 C24 C25 C31 C26 C31 C27 C30 Angle/° 177.6(2) 119.94(16) 120.62(16) 119.44(17) 179.8(2) 119.67(17) 124.19(17) 116.12(16) 173.5(2) 124.97(18) 107.16(18) 127.85(18) 110.48(17) 108.84(18) 105.95(18) 125.88(19) 128.16(18) 107.57(17) 123.77(19) 128.66(18) 130.37(19) 116.40(17) 124.70(18) 118.80(17) 131.79(18) 131.7(2) Atom C24 C24 C29 Atom C30 C30 C30 Atom C29 C34 C34 Angle/° 124.60(19) 119.86(18) 115.53(19) Atom C27 C33 C33 Atom C31 C31 C31 Atom C32 C27 C32 Angle/° 114.23(17) 109.58(16) 110.02(17) Table 5: Hydrogen Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 20240409TR_GA_CN5. Ueq is defined as 1/3 of the trace of the orthogonalised Uij. Atom x -179.2 -1882.27 293.24 -1734.38 -1138 1331.03 2925.79 2000.03 3145.92 4594.74 5264.14 5764.62 205.39 1835.51 1125.55 273.35 -931.33 1314.34 H20A H20B H20C H22 H23 H26 H28 H29 H31 H32A H32B H32C H33A H33B H33C H34A H34B H34C y 6623.98 5617.02 5817.37 2606.47 883.69 6555.56 4899.49 2513.26 8055.63 7053.47 8682.54 7282.83 7732.63 8868.74 7185.17 47.11 236.55 299.06 z 6551.64 5941.33 5729.12 5647.37 6559.08 7621.28 9484.26 9132.26 8599.42 9953.69 9725.71 9200.69 9160.52 9754.67 9900.48 7491.14 8236.6 8360.22 Ueq 48 48 48 38 33 32 35 35 37 47 47 47 59 59 59 56 56 56 Table 6: Atomic Occupancies for all atoms that are not fully occupied in 20240409TR_GA_CN5. Atom F3 F4 F5 Occupancy 0.801(11) 0.801(11) 0.801(11) Atom F4A F3A F5A Occupancy 0.199(11) 0.199(11) 0.199(11) Citations O.V. Dolomanov and L.J. Bourhis and R.J. Gildea and J.A.K. Howard and H. Puschmann, Olex2: A complete structure solution, refinement and analysis program, J. Appl. Cryst., (2009), 42, 339-341.