The synthesis and crystal structure of 5-(trifluoromethyl)-1,3,4-thiadiazol-2(3H)-one, a heterocycle of importance as a pharmaceutical building block, are presented.
Keywords: 1,3,4-thiadiazole; heterocycle; high Z′; Z′ = 6; hydrogen bonding; disorder; crystal structure
Abstract
The synthesis and crystal structure of C3HF3N2OS, systematic name 5-(trifluoromethyl)-1,3,4-thiadiazol-2(3H)-one (5-TMD-2-one), a compound containing the pharmacologically important heterocycle 1,3,4-thiadiazole, is presented. The asymmetric unit comprises six independent molecules (Z′ = 6), all of which are planar. The r.m.s. deviations from each mean plane range from 0.0063 to 0.0381 Å, not including the CF3 fluorine atoms. Within the crystal, two of the molecules form hydrogen-bonded dimers that in turn combine with inversion-related copies to form tetrameric constructs. Similar tetramers, but lacking inversion symmetry, are formed by the remaining four molecules. The tetramers are linked into tape-like motifs by S⋯O and O⋯O close contacts. The environments of each symmetry-independent molecule were compared via a Hirshfeld surface analysis. The most abundant atom–atom contacts are between fluorine atoms, while the strongest result from N—H⋯O hydrogen bonds.
1. Chemical context
The 1,3,4-thiadiazole ring is a pharmacologically important heterocycle found in compounds covering a broad spectrum of bioactivity (Moussa et al., 2023 ▸). Recent reviews have highlighted the beneficial properties of 1,3,4-thiadiazole derivatives, including microbiological activity (Barbosa & de Aguiar, 2019 ▸) and their potential use as scaffolds for drug design and development (Han et al., 2021 ▸). A series of 2,5-disubstituted 1,3,4-thiadiazole derivatives were synthesized and investigated for antituberculosis structure–activity relationships by Oruç et al. (2004 ▸). The structures and thermal behaviour of substituted 1,3,4-thiadiazole organic crystals have been investigated by Shen et al. (2005 ▸). Reviews of progress covering the biological activities of 1,3,4-thiadiazole and its derivatives were reported by Jain et al. (2013 ▸) and by Anthwal et al. (2022 ▸). Their use as scaffolds for promising antimicrobial agents (Serban et al., 2018 ▸) and anti-cancer agents (Çevik et al., 2020 ▸) have also been published. The interplay of inter- and intramolecular interactions in the crystal structures of 1,3,4-thiadiazole resorcinol derivatives was reported by Hoser et al. (2018 ▸). A series of four biologically active 2-benzamido-5-(4-fluoro-3-phenoxyphenyl)-1,3,4-thiadiazoles derivatives were synthesized by Panini et al. (2013 ▸) and their crystal structures studied to evaluate the effects of systematic variations in the functional group attached at the para position of the benzamido ring. Lastly, the crystal structures of three 6-aryl-2-(4-chlorobenzyl)-5-[(1H-indol-3-yl)methyl]imidazo[2,1-b][1,3,4]thiadiazoles were reported by Shamanth et al. (2020 ▸).
Overall, the 1,3,4-thiadiazole heterocycle provides the basis of a promising area of research in medicinal chemistry and drug discovery, with a wide range of potential applications. The reported findings provide insights into the molecular properties and biological activities of 1,3,4-thiadiazole derivatives, contributing to the development of novel therapeutic agents. With the importance of 1,3,4-thiadiazoles in drug discovery research in mind, this paper reports the synthesis and crystal structure of 5-(trifluoromethyl)-1,3,4-thiadiazol-2(3H)-one, C3HF3N2OS (5-TMD-2-one).
2. Structural commentary
The molecular structure of 5-TMD-2-one consists of a 1,3,4-thiadiazone ring, essentially a flat pentagonal heterocycle with two adjacent nitrogen atoms, each flanked by carbon atoms, with a sulfur atom completing the ring. The simplicity of the molecular structure notwithstanding, the crystal structure of 5-TMD-2-one is far more complex, as the asymmetric unit contains six molecules (Z′ = 6; designated A–F in Fig. 1 ▸). In each molecule, one of the nitrogen atoms (N1) carries a hydrogen atom and is single bonded to C1, while N2 is double bonded to C2. Atom C1 forms a carbonyl group with O1, and C2 carries a trifluoromethyl substituent. Deviations (r.m.s.) from planarity range from 0.0063 Å in molecule B to 0.0381 Å in molecule D, with the largest deviation for any atom (aside from fluorine), being 0.065 (8) Å for C3D, the trifluoromethyl carbon of molecule D. The only internal degree of freedom is the torsion of the trifluoromethyl group, which is disordered in all six symmetry-independent molecules in the structure. Indeed, the CF3 orientations and the refined occupancies of the disorder components, which range from 0.500 (5):0.500 (5) for molecule D to 0.908 (2):0.092 (2) for molecule F, are the only significant differences between the six molecules.
Figure 1.
An ellipsoid plot (30% probability) of the asymmetric unit of 5-TMD-2-one. The CF3 groups on all six independent molecules are disordered over two orientations, but only the major components are shown.
The crystals were observed to shatter when cooled to 90 K, but remained intact and gave sharp diffraction at 180 K. This observation prompted us to investigate whether warming the crystals might lead to a simpler crystal structure, i.e., with fewer molecules in the asymmetric unit. A crystal mounted at room temperature, however, indexed to give essentially the same unit cell and structure (again with Z′ = 6) as at 180 K.
3. Supramolecular features
The main supramolecular constructs in crystals of 5-TMD-2-one are hydrogen-bonded tetramers. There are, however, slight differences for tetramers formed by molecules A and B (with inversion-related copies) and by molecules C, D, E and F. Within the chosen asymmetric unit, molecules A and B are joined by one short N1A—H1A⋯O1B [dD–A
= 2.726 (2) Å] and one longer N1B—H1B⋯O1A [dD–A
= 3.328 (2) Å] hydrogen bond, leading to
(8) dimer motifs. Pairs of these dimers are connected to inversion-related copies by N1B—H1B⋯O1A
i [dD–A
= 2.955 (2) Å; symmetry code: (i) 2 − x, 1 − y, 1 − z] hydrogen bonds, producing
(4) motifs in which the hydrogen atoms act as bifurcated donors (Fig. 2 ▸), thereby generating tetramers. Adjacent tetramers of A and B molecules are in close contact [via S1B⋯O1B
ii = 2.9743 (14) Å and O1B⋯O1B
ii = 2.996 (3) Å; symmetry code: (ii) 1 − x, 1 − y, 1 − z] contacts, forming tape-like structures parallel to (011) that extend along the [100] direction. For molecules C, D, E and F, the individual motifs are similar (see Table 1 ▸), but lack the constraints of inversion symmetry, leading to tapes with a slightly V-shaped cross section, as shown in Fig. 3 ▸. Owing to the complexity, however, the overall packing is best viewed using a molecular graphics program such as Mercury (Macrae et al., 2020 ▸). Hydrogen bonding and close-contact distances are given in Table 1 ▸.
Figure 2.
A partial packing plot of 5-TMD-2-one viewed down the c-axis for the A and B molecules, showing N—H⋯O hydrogen bonds (dashed lines) and intermolecular contacts (S⋯O and O⋯O, dotted lines), forming a tape-like motif parallel to (011) that extends along the a-axis direction. The hydrogen bonding and intermolecular contacts for molecules C, D, E and F are similar, but lack crystallographically imposed inversion symmetry.
Table 1. Hydrogen bonds and other intermolecular contacts (Å, °) for 5-TMD-2-one.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N1A—H1A—O1B | 0.819 (16) | 1.918 (16) | 2.726 (2) | 169 (2) |
| N1B—H1B—O1A | 0.826 (15) | 2.574 (17) | 3.328 (2) | 152.3 (19) |
| N1B—H1B—O1A i | 0.826 (15) | 2.347 (19) | 2.955 (2) | 131.0 (18) |
| N1C—H1C—O1D | 0.829 (15) | 1.927 (16) | 2.7485 (19) | 171 (2) |
| N1D—H1D—O1C | 0.821 (15) | 2.605 (17) | 3.342 (2) | 150 (2) |
| N1D—H1D—O1F | 0.821 (15) | 2.280 (19) | 2.908 (2) | 134 (2) |
| N1E—H1E—O1C | 0.814 (15) | 2.262 (19) | 2.912 (2) | 137 (2) |
| N1E—H1E—O1F | 0.814 (15) | 2.643 (18) | 3.359 (2) | 148 (2) |
| N1F—H1F—O1E | 0.820 (16) | 1.952 (16) | 2.764 (2) | 171 (2) |
| S1B⋯O1B ii | 2.9743 (14) | |||
| O1B⋯O1B ii | 2.996 (3) | |||
| S1D⋯O1E iii | 3.0279 (14) | |||
| O1D⋯O1E iii | 3.0686 (18) | |||
| O1D⋯S1E iii | 3.0093 (14) |
Symmetry codes: (i) −x + 2, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z + 1; (iii) x − 1, y, z.
Figure 3.
A partial packing plot of 5-TMD-2-one viewed down the a-axis, showing the main difference between the A/B tape motif and those formed by molecules C, D, E and F, which have a shallow V-shaped cross section.
Atom–atom contact two-dimensional fingerprint plots calculated using CrystalExplorer (Spackman et al., 2021 ▸) for each of the six independent molecules show that their environments are similar (Fig. 4 ▸ a–f). The most abundant contacts in each case are F⋯F (shown in blue and green), ranging from 39.8% in molecule A (Fig. 4 ▸ a) to 25.6% in molecule E (Fig. 4 ▸ e).
Figure 4.
Hirshfeld surface two-dimensional fingerprint plots for each of the six independent molecules A–F [depicted in panels (a)–(f)] of 5-TMD-2-one. The F⋯F contacts, highlighted in blue and green have the greatest coverage. The N—H⋯O hydrogen bonds are apparent as grey spikes extending to the lower left in each panel. The longer, sharper spikes correspond to the shorter, stronger interactions in each case.
4. Database survey
A search of the Cambridge Structural Database (CSD, v5.43 with updates to November 2022; Groom et al., 2016 ▸) for ‘thiadiazole’ returned 2068 hits, while ‘1,3,4-thiadiazole’ gave 745 hits. A subsequent search using just the 1,3,4-thiadiazole ring fragment with ‘any substituent’ specified at the equivalent of C1, C2, and N1 produced 682 hits. This fragment, but with hydrogen attached to N1 gave 114 hits. A search with trifluoromethyl added at C2 gave no hits, while a search with ‘any oxygen-bound’ substituent on C1 returned only four hits. These are GAQVIF (Zhang et al., 2012 ▸), which is 5-methoxy-1,3,4-thiadiazol-2(3H)-one, LAPSAY (Kang et al., 2012a ▸), which is a DMSO solvate of 5,5′-[1,4-phenylenebis(methylenesulfanediyl)]bis[1,3,4-thiadiazol-2(3H)-one], and triclinic (YAXWAX: Kang et al., 2012b ▸) and monoclinic (YAXWAX01: Kim & Kang, 2014 ▸) polymorphs of 5-amino-1,3,4-thiadiazol-2(3H)-one.
A few other crystal structures of compounds related to 5-TMD-2-one include MAZZIX and NIYDOO01 (Boechat et al., 2006 ▸), 1,3,4-thiadiazolium-2-thiolate (Hu et al., 2006 ▸) and 3-(mercaptomethyl)-1,3,4-thiadiazol-2(3H)-one (HORZAQ; Hartung et al., 2009 ▸).
Although crystal structures with Z′ > 1 are not uncommon, their scarcity increases with Z′. In a detailed survey of structures with high Z′, Brock (2016 ▸) estimated that only about 12% of structures in the Cambridge Structural Database at the time (CSD; Groom et al., 2016 ▸) had Z′ > 1, and < 0.1% had Z′ > 4. Without any attempt to filter duplicates or pathological cases, in the current version of the CSD (v5.43, vide supra) there are 655 entries with Z′ = 6 out of over 1.2 million (∼0.05%), so by this criterion alone, the structure of 5-TMD-2-one is unusual, though not unprecedented.
5. Synthesis, crystallization and spectroscopic details
Synthesis of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole
To a clean and dry 1 L round-bottom flask, 14.5 g of thiosemicarbazide suspended in 500 ml of 1,4 dioxane was added, with stirring. 12.0 ml of CF3COOH and 15.0 mL of POCl3 were slowly added over about 30 min. The reaction was maintained for 3 h, during which time, a large amount of HCl gas was produced. After completion of HCl gas liberation, the reaction mixture was poured into 100 mL of cold water with stirring and the pH adjusted to 9 with 50% NaOH solution, to give a solid precipitate. The product, 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, was filtered, washed with cold water and dried at 363 K (20.6 g).
Synthesis of 5-TMD-2-one
In a 250 ml round-bottomed flask, 20.6 g of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole was suspended with 150 ml conc. hydrochloric acid, with stirring. The reaction mixture was cooled to between 263 and 268 K. Then, 350 mL of aqueous NaNO2 were added slowly (21.2 g, 0.307 mol, 4 eq.) while maintaining the temperature at 263–268 K with continued stirring. After 2 h, 100 ml of H2O were added with warming up to 333–353 K and stirred for a further 3 h. The reaction mixture was then cooled to room temperature, 150 mL of CH2Cl2 were added, the organic layer separated and a further 150 ml CH2Cl2 were added. The combined organic layers were washed with water twice and dried with sodium sulfate, then finally distilled completely. The crude product was purified by chromatography over SiO2 (hexane:EtOAc, 9:1). The resulting product, pure 5-TMD-2-one (12.5 g) was recrystallized from hexane. MS m/z: 169.12 (M − H)+.
A generalized reaction scheme is presented in Fig. 5 ▸.
Figure 5.
A general scheme for the synthesis of 5-TMD-2-one.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All hydrogen atoms were found in difference-Fourier maps. Their coordinates were refined freely with U iso parameters set to 1.2U eq of their attached nitrogen atom. To ensure satisfactory refinement of the disordered CF3 groups, a combination of constraints (EADP in SHELXL) and restraints (SHELXL commands SAME, SADI, SIMU, and RIGU) were employed.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C3HF3N2OS |
| M r | 170.12 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 180 |
| a, b, c (Å) | 10.8996 (7), 13.9700 (8), 14.1351 (9) |
| α, β, γ (°) | 63.253 (2), 71.160 (2), 67.954 (2) |
| V (Å3) | 1750.38 (19) |
| Z | 12 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.54 |
| Crystal size (mm) | 0.32 × 0.29 × 0.28 |
| Data collection | |
| Diffractometer | Bruker D8 Venture dual source |
| Absorption correction | Multi-scan (SADABS; Krause et al., 2015 ▸) |
| T min, T max | 0.922, 0.971 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 52212, 8021, 6646 |
| R int | 0.045 |
| (sin θ/λ)max (Å−1) | 0.650 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.037, 0.090, 1.02 |
| No. of reflections | 8021 |
| No. of parameters | 728 |
| No. of restraints | 273 |
| H-atom treatment | Only H-atom coordinates refined |
| Δρmax, Δρmin (e Å−3) | 0.41, −0.31 |
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023004267/vm2283sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023004267/vm2283Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989023004267/vm2283Isup3.cml
CCDC reference: 2263179
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
DG is grateful to the DOS in Chemistry, University of Mysore, for providing research facilities. HSY thanks UGC for a BSR Faculty fellowship for three years.
supplementary crystallographic information
Crystal data
| C3HF3N2OS | Z = 12 |
| Mr = 170.12 | F(000) = 1008 |
| Triclinic, P1 | Dx = 1.937 Mg m−3 |
| a = 10.8996 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 13.9700 (8) Å | Cell parameters from 9954 reflections |
| c = 14.1351 (9) Å | θ = 2.4–33.1° |
| α = 63.253 (2)° | µ = 0.54 mm−1 |
| β = 71.160 (2)° | T = 180 K |
| γ = 67.954 (2)° | Block, colourless |
| V = 1750.38 (19) Å3 | 0.32 × 0.29 × 0.28 mm |
Data collection
| Bruker D8 Venture dual source diffractometer | 8021 independent reflections |
| Radiation source: microsource | 6646 reflections with I > 2σ(I) |
| Detector resolution: 7.41 pixels mm-1 | Rint = 0.045 |
| φ and ω scans | θmax = 27.5°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −14→14 |
| Tmin = 0.922, Tmax = 0.971 | k = −17→18 |
| 52212 measured reflections | l = −18→18 |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.037 | Only H-atom coordinates refined |
| wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0319P)2 + 1.258P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max = 0.001 |
| 8021 reflections | Δρmax = 0.41 e Å−3 |
| 728 parameters | Δρmin = −0.31 e Å−3 |
| 273 restraints | Extinction correction: SHELXL2019/2 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0078 (13) |
Special details
| Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998). The crystals appeared to undergo a destructive phase transition when cooled to 90K. Visual inspection of crystal integrity and diffraction quality vs temperature established a safe temperature for data collection of -93° C. |
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
| Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| S1A | 0.96653 (5) | 0.22146 (4) | 0.77875 (4) | 0.03426 (12) | |
| O1A | 0.95363 (14) | 0.40427 (12) | 0.59471 (11) | 0.0408 (3) | |
| N1A | 0.76657 (16) | 0.34097 (14) | 0.68704 (13) | 0.0350 (4) | |
| H1A | 0.720 (2) | 0.3890 (16) | 0.6429 (16) | 0.042* | |
| N2A | 0.71853 (16) | 0.25921 (14) | 0.77307 (13) | 0.0365 (4) | |
| C1A | 0.89728 (18) | 0.33853 (15) | 0.66966 (14) | 0.0286 (4) | |
| C2A | 0.81231 (18) | 0.19210 (15) | 0.82619 (14) | 0.0294 (4) | |
| C3A | 0.7884 (12) | 0.0917 (7) | 0.9244 (7) | 0.0411 (6) | 0.731 (9) |
| F1A | 0.8079 (7) | 0.0963 (5) | 1.0078 (2) | 0.1020 (18) | 0.731 (9) |
| F2A | 0.8728 (5) | 0.0021 (2) | 0.9115 (4) | 0.1037 (19) | 0.731 (9) |
| F3A | 0.6673 (3) | 0.0848 (4) | 0.9448 (4) | 0.0895 (16) | 0.731 (9) |
| C3A' | 0.792 (3) | 0.0889 (17) | 0.9217 (17) | 0.0411 (6) | 0.269 (9) |
| F1A' | 0.7891 (17) | 0.0107 (7) | 0.8980 (6) | 0.081 (4) | 0.269 (9) |
| F2A' | 0.6812 (11) | 0.1049 (7) | 0.9895 (8) | 0.084 (4) | 0.269 (9) |
| F3A' | 0.8842 (9) | 0.0400 (8) | 0.9797 (8) | 0.068 (3) | 0.269 (9) |
| S1B | 0.55246 (4) | 0.65799 (4) | 0.34668 (4) | 0.03139 (12) | |
| O1B | 0.63289 (14) | 0.48600 (12) | 0.52132 (12) | 0.0451 (4) | |
| N1B | 0.77624 (15) | 0.59413 (13) | 0.40477 (12) | 0.0291 (3) | |
| H1B | 0.8414 (18) | 0.5583 (16) | 0.4356 (16) | 0.035* | |
| N2B | 0.78780 (15) | 0.68295 (13) | 0.31098 (12) | 0.0313 (3) | |
| C1B | 0.65984 (18) | 0.56361 (15) | 0.44064 (15) | 0.0300 (4) | |
| C2B | 0.67908 (18) | 0.72306 (15) | 0.27328 (14) | 0.0291 (4) | |
| C3B | 0.6649 (7) | 0.8230 (4) | 0.1690 (4) | 0.0376 (6) | 0.802 (7) |
| F1B | 0.5873 (4) | 0.8191 (3) | 0.1169 (2) | 0.0688 (9) | 0.802 (7) |
| F2B | 0.6098 (5) | 0.91515 (18) | 0.1856 (2) | 0.0919 (15) | 0.802 (7) |
| F3B | 0.7804 (2) | 0.8280 (3) | 0.1034 (2) | 0.0872 (14) | 0.802 (7) |
| C3B' | 0.657 (3) | 0.8255 (15) | 0.1755 (15) | 0.0376 (6) | 0.198 (7) |
| F1B' | 0.7410 (13) | 0.8816 (9) | 0.152 (1) | 0.069 (4) | 0.198 (7) |
| F2B' | 0.6675 (19) | 0.8020 (9) | 0.0960 (8) | 0.076 (4) | 0.198 (7) |
| F3B' | 0.5395 (10) | 0.8927 (9) | 0.1870 (9) | 0.073 (3) | 0.198 (7) |
| S1C | 0.51557 (5) | 0.34764 (4) | 1.01026 (4) | 0.03561 (13) | |
| O1C | 0.52164 (14) | 0.50625 (12) | 0.80892 (11) | 0.0396 (3) | |
| N1C | 0.33717 (16) | 0.43878 (13) | 0.89515 (13) | 0.0323 (4) | |
| H1C | 0.295 (2) | 0.4746 (17) | 0.8448 (15) | 0.039* | |
| N2C | 0.28288 (16) | 0.36498 (13) | 0.98623 (13) | 0.0338 (4) | |
| C1C | 0.46203 (18) | 0.44504 (15) | 0.88628 (14) | 0.0285 (4) | |
| C2C | 0.36572 (18) | 0.31244 (15) | 1.05150 (14) | 0.0297 (4) | |
| C3C | 0.3342 (8) | 0.2217 (5) | 1.1581 (4) | 0.0396 (6) | 0.789 (5) |
| F1C | 0.3650 (4) | 0.2303 (2) | 1.23606 (15) | 0.0761 (10) | 0.789 (5) |
| F2C | 0.4036 (4) | 0.12531 (17) | 1.1556 (2) | 0.0997 (16) | 0.789 (5) |
| F3C | 0.2062 (2) | 0.2288 (3) | 1.1867 (2) | 0.0937 (14) | 0.789 (5) |
| C3C' | 0.335 (3) | 0.2182 (18) | 1.1521 (14) | 0.0396 (6) | 0.211 (5) |
| F1C' | 0.2788 (13) | 0.1565 (8) | 1.1434 (6) | 0.069 (3) | 0.211 (5) |
| F2C' | 0.2543 (14) | 0.2491 (6) | 1.2276 (7) | 0.079 (4) | 0.211 (5) |
| F3C' | 0.4371 (9) | 0.1531 (10) | 1.1961 (9) | 0.084 (4) | 0.211 (5) |
| S1D | 0.12479 (5) | 0.74725 (4) | 0.55582 (4) | 0.03674 (13) | |
| O1D | 0.22315 (13) | 0.56130 (11) | 0.71384 (11) | 0.0359 (3) | |
| N1D | 0.34765 (15) | 0.68830 (13) | 0.61291 (13) | 0.0316 (3) | |
| H1D | 0.4136 (18) | 0.6541 (17) | 0.6423 (17) | 0.038* | |
| N2D | 0.34835 (16) | 0.78693 (14) | 0.52875 (13) | 0.0367 (4) | |
| C1D | 0.23960 (18) | 0.64841 (15) | 0.64245 (14) | 0.0280 (4) | |
| C2D | 0.2393 (2) | 0.82565 (16) | 0.49213 (15) | 0.0343 (4) | |
| C3D | 0.2279 (17) | 0.9296 (11) | 0.3921 (11) | 0.0446 (16) | 0.499 (5) |
| F1D | 0.2101 (9) | 1.0139 (4) | 0.4116 (5) | 0.112 (3) | 0.499 (5) |
| F2D | 0.3266 (4) | 0.9244 (3) | 0.3131 (3) | 0.0764 (15) | 0.499 (5) |
| F3D | 0.1208 (4) | 0.9442 (4) | 0.3547 (4) | 0.087 (2) | 0.499 (5) |
| C3D' | 0.2036 (17) | 0.9381 (11) | 0.4023 (11) | 0.0446 (16) | 0.501 (5) |
| F1D' | 0.2156 (10) | 0.9282 (4) | 0.3157 (3) | 0.116 (3) | 0.501 (5) |
| F2D' | 0.0860 (4) | 1.0024 (3) | 0.4237 (4) | 0.0802 (16) | 0.501 (5) |
| F3D' | 0.2875 (4) | 0.9973 (4) | 0.3863 (5) | 0.0759 (18) | 0.501 (5) |
| S1E | 1.01005 (4) | 0.44778 (4) | 0.86856 (4) | 0.03126 (12) | |
| O1E | 0.94784 (14) | 0.58947 (12) | 0.67573 (11) | 0.0405 (3) | |
| N1E | 0.79039 (15) | 0.50383 (13) | 0.80787 (13) | 0.0314 (3) | |
| H1E | 0.7261 (19) | 0.5320 (17) | 0.7778 (17) | 0.038* | |
| N2E | 0.77016 (15) | 0.42897 (13) | 0.91058 (13) | 0.0312 (3) | |
| C1E | 0.91157 (18) | 0.52690 (15) | 0.76578 (15) | 0.0293 (4) | |
| C2E | 0.87636 (18) | 0.39383 (14) | 0.95031 (14) | 0.0280 (4) | |
| C3E | 0.8872 (13) | 0.3062 (9) | 1.0617 (6) | 0.0361 (6) | 0.69 (3) |
| F1E | 0.9321 (9) | 0.3380 (7) | 1.1172 (7) | 0.0522 (13) | 0.69 (3) |
| F2E | 0.9686 (10) | 0.2101 (6) | 1.0618 (7) | 0.0684 (17) | 0.69 (3) |
| F3E | 0.7664 (7) | 0.2929 (10) | 1.1172 (8) | 0.0677 (19) | 0.69 (3) |
| C3E' | 0.880 (3) | 0.308 (2) | 1.0615 (14) | 0.0361 (6) | 0.31 (3) |
| F1E' | 0.926 (3) | 0.2096 (11) | 1.0533 (14) | 0.072 (4) | 0.31 (3) |
| F2E' | 0.7658 (15) | 0.3082 (18) | 1.1266 (18) | 0.051 (3) | 0.31 (3) |
| F3E' | 0.965 (2) | 0.312 (2) | 1.1065 (16) | 0.063 (4) | 0.31 (3) |
| S1F | 0.58836 (5) | 0.88473 (4) | 0.44640 (4) | 0.03321 (12) | |
| O1F | 0.62033 (14) | 0.68089 (11) | 0.60648 (11) | 0.0388 (3) | |
| N1F | 0.79719 (17) | 0.75904 (14) | 0.52504 (13) | 0.0367 (4) | |
| H1F | 0.849 (2) | 0.7086 (16) | 0.5639 (17) | 0.044* | |
| N2F | 0.83663 (16) | 0.85025 (14) | 0.44911 (13) | 0.0364 (4) | |
| C1F | 0.66894 (18) | 0.75638 (15) | 0.54119 (14) | 0.0296 (4) | |
| C2F | 0.73824 (18) | 0.92081 (15) | 0.40304 (14) | 0.0298 (4) | |
| C3F | 0.7544 (3) | 1.0293 (2) | 0.3131 (2) | 0.0362 (5) | 0.908 (2) |
| F1F | 0.7885 (3) | 1.02172 (14) | 0.21920 (11) | 0.0763 (7) | 0.908 (2) |
| F2F | 0.64084 (16) | 1.11017 (12) | 0.31281 (15) | 0.0615 (5) | 0.908 (2) |
| F3F | 0.84528 (19) | 1.06373 (14) | 0.32310 (15) | 0.0662 (5) | 0.908 (2) |
| C3F' | 0.759 (2) | 1.0237 (17) | 0.3096 (18) | 0.0362 (5) | 0.092 (2) |
| F1F' | 0.718 (3) | 1.1043 (14) | 0.3427 (12) | 0.0763 (7) | 0.092 (2) |
| F2F' | 0.8847 (15) | 1.0179 (13) | 0.2641 (15) | 0.0615 (5) | 0.092 (2) |
| F3F' | 0.6761 (19) | 1.0648 (15) | 0.2436 (15) | 0.0662 (5) | 0.092 (2) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1A | 0.0256 (2) | 0.0354 (2) | 0.0310 (2) | −0.01036 (19) | −0.00812 (18) | 0.00015 (19) |
| O1A | 0.0352 (7) | 0.0419 (8) | 0.0344 (7) | −0.0201 (6) | −0.0069 (6) | 0.0029 (6) |
| N1A | 0.0300 (8) | 0.0348 (8) | 0.0300 (8) | −0.0151 (7) | −0.0127 (7) | 0.0062 (7) |
| N2A | 0.0319 (8) | 0.0372 (9) | 0.0322 (8) | −0.0176 (7) | −0.0099 (7) | 0.0031 (7) |
| C1A | 0.0299 (9) | 0.0288 (8) | 0.0245 (8) | −0.0112 (7) | −0.0072 (7) | −0.0036 (7) |
| C2A | 0.0290 (9) | 0.0304 (9) | 0.0245 (8) | −0.0118 (7) | −0.0056 (7) | −0.0033 (7) |
| C3A | 0.0385 (12) | 0.0386 (11) | 0.0327 (11) | −0.0159 (10) | −0.0089 (9) | 0.0040 (9) |
| F1A | 0.176 (5) | 0.108 (3) | 0.0278 (12) | −0.085 (3) | −0.0336 (19) | 0.0169 (14) |
| F2A | 0.094 (3) | 0.0308 (12) | 0.099 (3) | −0.0039 (15) | 0.022 (2) | 0.0103 (13) |
| F3A | 0.0565 (16) | 0.088 (2) | 0.080 (3) | −0.0527 (17) | −0.0287 (16) | 0.0425 (19) |
| C3A' | 0.0385 (12) | 0.0386 (11) | 0.0327 (11) | −0.0159 (10) | −0.0089 (9) | 0.0040 (9) |
| F1A' | 0.16 (1) | 0.047 (4) | 0.042 (3) | −0.057 (5) | −0.021 (5) | 0.004 (3) |
| F2A' | 0.064 (5) | 0.046 (4) | 0.061 (5) | −0.005 (4) | 0.027 (4) | 0.012 (3) |
| F3A' | 0.064 (5) | 0.060 (5) | 0.058 (5) | −0.034 (4) | −0.039 (4) | 0.027 (3) |
| S1B | 0.0244 (2) | 0.0297 (2) | 0.0311 (2) | −0.01107 (18) | −0.01094 (18) | 0.00303 (18) |
| O1B | 0.0392 (8) | 0.0442 (8) | 0.0402 (8) | −0.0244 (7) | −0.0213 (6) | 0.0140 (6) |
| N1B | 0.0224 (7) | 0.0317 (8) | 0.0298 (8) | −0.0101 (6) | −0.0082 (6) | −0.0042 (6) |
| N2B | 0.0282 (8) | 0.0332 (8) | 0.0295 (8) | −0.0137 (6) | −0.0034 (6) | −0.0064 (6) |
| C1B | 0.0263 (9) | 0.0291 (9) | 0.0309 (9) | −0.0097 (7) | −0.0121 (7) | −0.0017 (7) |
| C2B | 0.0290 (9) | 0.0269 (8) | 0.0277 (9) | −0.0118 (7) | −0.0036 (7) | −0.0048 (7) |
| C3B | 0.0402 (13) | 0.034 (1) | 0.0306 (11) | −0.0157 (9) | −0.0072 (10) | −0.0006 (9) |
| F1B | 0.085 (2) | 0.0696 (17) | 0.0473 (14) | −0.0416 (16) | −0.0370 (14) | 0.0152 (11) |
| F2B | 0.176 (4) | 0.0276 (10) | 0.0484 (13) | −0.0149 (16) | −0.024 (2) | −0.0022 (9) |
| F3B | 0.0469 (12) | 0.091 (2) | 0.0511 (15) | −0.0233 (12) | 0.0028 (10) | 0.0301 (14) |
| C3B' | 0.0402 (13) | 0.034 (1) | 0.0306 (11) | −0.0157 (9) | −0.0072 (10) | −0.0006 (9) |
| F1B' | 0.075 (7) | 0.056 (6) | 0.063 (6) | −0.049 (5) | −0.037 (5) | 0.032 (4) |
| F2B' | 0.137 (11) | 0.053 (5) | 0.036 (4) | −0.018 (7) | −0.029 (6) | −0.013 (4) |
| F3B' | 0.060 (5) | 0.035 (5) | 0.070 (6) | 0.005 (3) | −0.017 (4) | 0.014 (4) |
| S1C | 0.0280 (2) | 0.0413 (3) | 0.0296 (2) | −0.0141 (2) | −0.01040 (18) | 0.0006 (2) |
| O1C | 0.0328 (7) | 0.0437 (8) | 0.0311 (7) | −0.0191 (6) | −0.0046 (6) | 0.0013 (6) |
| N1C | 0.0303 (8) | 0.0344 (8) | 0.0259 (8) | −0.0143 (7) | −0.0109 (6) | 0.0024 (6) |
| N2C | 0.0308 (8) | 0.0344 (8) | 0.0306 (8) | −0.0151 (7) | −0.0078 (7) | −0.0010 (7) |
| C1C | 0.0263 (9) | 0.0291 (9) | 0.0264 (9) | −0.0092 (7) | −0.0057 (7) | −0.0054 (7) |
| C2C | 0.0271 (9) | 0.0294 (9) | 0.0275 (9) | −0.0097 (7) | −0.0047 (7) | −0.0049 (7) |
| C3C | 0.0377 (11) | 0.0379 (11) | 0.0316 (12) | −0.0139 (9) | −0.0066 (9) | −0.0003 (9) |
| F1C | 0.112 (2) | 0.0858 (19) | 0.0287 (10) | −0.0521 (18) | −0.0219 (12) | 0.0062 (10) |
| F2C | 0.151 (4) | 0.0261 (10) | 0.0597 (17) | −0.0153 (14) | 0.0255 (19) | −0.002 (1) |
| F3C | 0.0472 (12) | 0.113 (3) | 0.0635 (18) | −0.0458 (14) | −0.0143 (11) | 0.0371 (16) |
| C3C' | 0.0377 (11) | 0.0379 (11) | 0.0316 (12) | −0.0139 (9) | −0.0066 (9) | −0.0003 (9) |
| F1C' | 0.111 (8) | 0.062 (5) | 0.043 (4) | −0.066 (6) | −0.015 (5) | 0.007 (3) |
| F2C' | 0.114 (8) | 0.039 (4) | 0.042 (4) | −0.018 (5) | 0.024 (5) | −0.008 (3) |
| F3C' | 0.052 (4) | 0.072 (7) | 0.066 (6) | −0.017 (4) | −0.027 (4) | 0.035 (5) |
| S1D | 0.0316 (2) | 0.0360 (3) | 0.0367 (3) | −0.0148 (2) | −0.0166 (2) | 0.0028 (2) |
| O1D | 0.0348 (7) | 0.0359 (7) | 0.0326 (7) | −0.0158 (6) | −0.0154 (6) | 0.0020 (6) |
| N1D | 0.0236 (8) | 0.0372 (8) | 0.0312 (8) | −0.0114 (7) | −0.0083 (6) | −0.0059 (7) |
| N2D | 0.0320 (8) | 0.0407 (9) | 0.0331 (9) | −0.0182 (7) | −0.0032 (7) | −0.0056 (7) |
| C1D | 0.0258 (9) | 0.0318 (9) | 0.0243 (8) | −0.0091 (7) | −0.0073 (7) | −0.0061 (7) |
| C2D | 0.0358 (10) | 0.0347 (10) | 0.0285 (9) | −0.0163 (8) | −0.0053 (8) | −0.0036 (8) |
| C3D | 0.044 (5) | 0.0404 (18) | 0.037 (2) | −0.019 (2) | −0.009 (2) | 0.0020 (16) |
| F1D | 0.234 (9) | 0.0336 (19) | 0.068 (3) | −0.025 (4) | −0.056 (5) | −0.0092 (19) |
| F2D | 0.064 (2) | 0.069 (2) | 0.0406 (18) | −0.0176 (18) | 0.0047 (16) | 0.0153 (15) |
| F3D | 0.064 (2) | 0.088 (3) | 0.066 (3) | −0.038 (2) | −0.040 (2) | 0.039 (2) |
| C3D' | 0.044 (5) | 0.0404 (18) | 0.037 (2) | −0.019 (2) | −0.009 (2) | 0.0020 (16) |
| F1D' | 0.255 (9) | 0.059 (2) | 0.038 (2) | −0.043 (5) | −0.054 (4) | −0.0030 (18) |
| F2D' | 0.060 (2) | 0.0460 (19) | 0.089 (3) | −0.0044 (15) | −0.0225 (19) | 0.0116 (18) |
| F3D' | 0.068 (2) | 0.047 (3) | 0.089 (4) | −0.035 (2) | −0.034 (2) | 0.023 (2) |
| S1E | 0.0248 (2) | 0.0340 (2) | 0.0298 (2) | −0.01272 (18) | −0.00930 (17) | −0.00089 (18) |
| O1E | 0.0323 (7) | 0.0462 (8) | 0.0326 (7) | −0.0175 (6) | −0.0125 (6) | 0.0039 (6) |
| N1E | 0.0236 (8) | 0.0353 (8) | 0.0323 (8) | −0.0104 (6) | −0.0086 (6) | −0.0059 (7) |
| N2E | 0.0262 (8) | 0.0325 (8) | 0.0331 (8) | −0.0121 (6) | −0.0028 (6) | −0.0095 (7) |
| C1E | 0.0244 (8) | 0.0299 (9) | 0.0305 (9) | −0.0088 (7) | −0.0084 (7) | −0.0053 (7) |
| C2E | 0.0268 (9) | 0.0265 (8) | 0.0299 (9) | −0.0113 (7) | −0.0033 (7) | −0.0080 (7) |
| C3E | 0.0355 (16) | 0.0319 (10) | 0.0338 (10) | −0.0124 (10) | −0.0049 (9) | −0.0047 (8) |
| F1E | 0.071 (3) | 0.053 (2) | 0.0369 (16) | −0.022 (2) | −0.020 (2) | −0.0093 (14) |
| F2E | 0.089 (4) | 0.0332 (16) | 0.049 (2) | 0.0112 (18) | −0.016 (2) | −0.0081 (13) |
| F3E | 0.048 (2) | 0.091 (5) | 0.041 (3) | −0.043 (3) | −0.0090 (19) | 0.014 (2) |
| C3E' | 0.0355 (16) | 0.0319 (10) | 0.0338 (10) | −0.0124 (10) | −0.0049 (9) | −0.0047 (8) |
| F1E' | 0.123 (10) | 0.023 (3) | 0.041 (4) | −0.013 (5) | −0.015 (6) | 0.004 (3) |
| F2E' | 0.048 (5) | 0.051 (4) | 0.033 (4) | −0.013 (4) | 0.010 (4) | −0.010 (3) |
| F3E' | 0.061 (6) | 0.076 (9) | 0.043 (5) | −0.038 (6) | −0.021 (5) | 0.009 (4) |
| S1F | 0.0259 (2) | 0.0324 (2) | 0.0338 (2) | −0.00987 (18) | −0.00592 (18) | −0.00442 (19) |
| O1F | 0.0346 (7) | 0.0387 (7) | 0.0349 (7) | −0.0186 (6) | −0.0050 (6) | −0.0010 (6) |
| N1F | 0.0307 (8) | 0.0396 (9) | 0.0290 (8) | −0.0158 (7) | −0.0110 (7) | 0.0047 (7) |
| N2F | 0.0332 (8) | 0.0418 (9) | 0.0283 (8) | −0.0187 (7) | −0.0079 (7) | 0.0001 (7) |
| C1F | 0.0286 (9) | 0.0327 (9) | 0.0247 (9) | −0.0110 (7) | −0.0046 (7) | −0.0065 (7) |
| C2F | 0.0305 (9) | 0.0348 (9) | 0.0225 (8) | −0.0144 (8) | −0.0032 (7) | −0.0060 (7) |
| C3F | 0.0387 (10) | 0.0366 (10) | 0.0297 (10) | −0.0167 (9) | −0.0051 (8) | −0.0052 (8) |
| F1F | 0.141 (2) | 0.0501 (9) | 0.0212 (7) | −0.0369 (11) | 0.0040 (9) | −0.0042 (6) |
| F2F | 0.0500 (9) | 0.0390 (8) | 0.0646 (11) | −0.0093 (7) | −0.0085 (8) | 0.0026 (7) |
| F3F | 0.0679 (11) | 0.0567 (10) | 0.0703 (11) | −0.0422 (9) | −0.0275 (9) | 0.0095 (8) |
| C3F' | 0.0387 (10) | 0.0366 (10) | 0.0297 (10) | −0.0167 (9) | −0.0051 (8) | −0.0052 (8) |
| F1F' | 0.141 (2) | 0.0501 (9) | 0.0212 (7) | −0.0369 (11) | 0.0040 (9) | −0.0042 (6) |
| F2F' | 0.0500 (9) | 0.0390 (8) | 0.0646 (11) | −0.0093 (7) | −0.0085 (8) | 0.0026 (7) |
| F3F' | 0.0679 (11) | 0.0567 (10) | 0.0703 (11) | −0.0422 (9) | −0.0275 (9) | 0.0095 (8) |
Geometric parameters (Å, º)
| S1A—C2A | 1.7279 (18) | S1D—C2D | 1.7262 (19) |
| S1A—C1A | 1.7825 (18) | S1D—C1D | 1.7728 (17) |
| O1A—C1A | 1.213 (2) | O1D—C1D | 1.214 (2) |
| N1A—C1A | 1.355 (2) | N1D—C1D | 1.355 (2) |
| N1A—N2A | 1.358 (2) | N1D—N2D | 1.357 (2) |
| N1A—H1A | 0.819 (16) | N1D—H1D | 0.821 (15) |
| N2A—C2A | 1.277 (2) | N2D—C2D | 1.279 (3) |
| C2A—C3A' | 1.497 (13) | C2D—C3D | 1.501 (9) |
| C2A—C3A | 1.500 (5) | C2D—C3D' | 1.516 (9) |
| C3A—F3A | 1.289 (12) | C3D—F1D | 1.26 (2) |
| C3A—F1A | 1.295 (12) | C3D—F2D | 1.284 (15) |
| C3A—F2A | 1.296 (12) | C3D—F3D | 1.34 (2) |
| C3A'—F3A' | 1.29 (3) | C3D'—F1D' | 1.25 (2) |
| C3A'—F2A' | 1.29 (3) | C3D'—F2D' | 1.293 (15) |
| C3A'—F1A' | 1.29 (3) | C3D'—F3D' | 1.35 (2) |
| S1B—C2B | 1.7251 (18) | S1E—C2E | 1.7262 (18) |
| S1B—C1B | 1.7725 (17) | S1E—C1E | 1.7764 (18) |
| O1B—C1B | 1.213 (2) | O1E—C1E | 1.214 (2) |
| N1B—N2B | 1.357 (2) | N1E—C1E | 1.357 (2) |
| N1B—C1B | 1.358 (2) | N1E—N2E | 1.360 (2) |
| N1B—H1B | 0.826 (15) | N1E—H1E | 0.814 (15) |
| N2B—C2B | 1.282 (2) | N2E—C2E | 1.281 (2) |
| C2B—C3B' | 1.481 (15) | C2E—C3E' | 1.490 (13) |
| C2B—C3B | 1.509 (4) | C2E—C3E | 1.506 (6) |
| C3B—F2B | 1.294 (7) | C3E—F2E | 1.301 (12) |
| C3B—F3B | 1.305 (7) | C3E—F3E | 1.329 (11) |
| C3B—F1B | 1.317 (7) | C3E—F1E | 1.333 (12) |
| C3B'—F2B' | 1.27 (2) | C3E'—F2E' | 1.29 (2) |
| C3B'—F3B' | 1.28 (2) | C3E'—F3E' | 1.31 (2) |
| C3B'—F1B' | 1.29 (2) | C3E'—F1E' | 1.32 (3) |
| S1C—C2C | 1.7261 (18) | S1F—C2F | 1.7297 (18) |
| S1C—C1C | 1.7835 (18) | S1F—C1F | 1.7881 (18) |
| O1C—C1C | 1.211 (2) | O1F—C1F | 1.213 (2) |
| N1C—N2C | 1.357 (2) | N1F—C1F | 1.354 (2) |
| N1C—C1C | 1.358 (2) | N1F—N2F | 1.357 (2) |
| N1C—H1C | 0.829 (15) | N1F—H1F | 0.820 (16) |
| N2C—C2C | 1.279 (2) | N2F—C2F | 1.275 (2) |
| C2C—C3C' | 1.485 (14) | C2F—C3F' | 1.484 (17) |
| C2C—C3C | 1.506 (4) | C2F—C3F | 1.505 (3) |
| C3C—F2C | 1.283 (8) | C3F—F1F | 1.300 (4) |
| C3C—F3C | 1.299 (8) | C3F—F3F | 1.319 (4) |
| C3C—F1C | 1.317 (7) | C3F—F2F | 1.326 (4) |
| C3C'—F2C' | 1.27 (2) | C3F'—F1F' | 1.28 (2) |
| C3C'—F3C' | 1.28 (2) | C3F'—F3F' | 1.30 (2) |
| C3C'—F1C' | 1.29 (2) | C3F'—F2F' | 1.30 (2) |
| C2A—S1A—C1A | 88.14 (8) | C2D—S1D—C1D | 87.99 (9) |
| C1A—N1A—N2A | 119.32 (15) | C1D—N1D—N2D | 118.36 (15) |
| C1A—N1A—H1A | 119.3 (16) | C1D—N1D—H1D | 122.7 (16) |
| N2A—N1A—H1A | 121.2 (16) | N2D—N1D—H1D | 118.9 (16) |
| C2A—N2A—N1A | 109.19 (15) | C2D—N2D—N1D | 109.65 (15) |
| O1A—C1A—N1A | 126.00 (17) | O1D—C1D—N1D | 127.28 (16) |
| O1A—C1A—S1A | 127.78 (15) | O1D—C1D—S1D | 125.59 (14) |
| N1A—C1A—S1A | 106.22 (12) | N1D—C1D—S1D | 107.14 (13) |
| N2A—C2A—C3A' | 121.6 (12) | N2D—C2D—C3D | 117.0 (8) |
| N2A—C2A—C3A | 120.8 (5) | N2D—C2D—C3D' | 123.4 (8) |
| N2A—C2A—S1A | 117.06 (14) | N2D—C2D—S1D | 116.86 (14) |
| C3A'—C2A—S1A | 121.2 (12) | C3D—C2D—S1D | 125.9 (9) |
| C3A—C2A—S1A | 122.1 (5) | C3D'—C2D—S1D | 119.7 (8) |
| F3A—C3A—F1A | 107.9 (8) | F1D—C3D—F2D | 110.1 (14) |
| F3A—C3A—F2A | 109.2 (8) | F1D—C3D—F3D | 108.4 (10) |
| F1A—C3A—F2A | 107.7 (8) | F2D—C3D—F3D | 103.9 (14) |
| F3A—C3A—C2A | 112.0 (7) | F1D—C3D—C2D | 111.5 (13) |
| F1A—C3A—C2A | 110.0 (7) | F2D—C3D—C2D | 114.5 (9) |
| F2A—C3A—C2A | 109.9 (7) | F3D—C3D—C2D | 107.9 (12) |
| F3A'—C3A'—F2A' | 104.3 (17) | F1D'—C3D'—F2D' | 109.6 (14) |
| F3A'—C3A'—F1A' | 103.3 (17) | F1D'—C3D'—F3D' | 108.4 (10) |
| F2A'—C3A'—F1A' | 104.3 (18) | F2D'—C3D'—F3D' | 102.7 (14) |
| F3A'—C3A'—C2A | 115.2 (19) | F1D'—C3D'—C2D | 111.5 (13) |
| F2A'—C3A'—C2A | 114.1 (18) | F2D'—C3D'—C2D | 114.9 (9) |
| F1A'—C3A'—C2A | 114.4 (18) | F3D'—C3D'—C2D | 109.0 (13) |
| C2B—S1B—C1B | 87.86 (8) | C2E—S1E—C1E | 88.10 (8) |
| N2B—N1B—C1B | 118.20 (15) | C1E—N1E—N2E | 118.65 (15) |
| N2B—N1B—H1B | 119.2 (15) | C1E—N1E—H1E | 126.0 (16) |
| C1B—N1B—H1B | 122.4 (15) | N2E—N1E—H1E | 115.3 (16) |
| C2B—N2B—N1B | 109.50 (15) | C2E—N2E—N1E | 109.35 (15) |
| O1B—C1B—N1B | 127.14 (16) | O1E—C1E—N1E | 127.58 (17) |
| O1B—C1B—S1B | 125.52 (14) | O1E—C1E—S1E | 125.56 (14) |
| N1B—C1B—S1B | 107.33 (12) | N1E—C1E—S1E | 106.86 (13) |
| N2B—C2B—C3B' | 122.3 (10) | N2E—C2E—C3E' | 119.3 (11) |
| N2B—C2B—C3B | 120.5 (3) | N2E—C2E—C3E | 121.9 (5) |
| N2B—C2B—S1B | 117.11 (14) | N2E—C2E—S1E | 117.02 (14) |
| C3B'—C2B—S1B | 120.5 (10) | C3E'—C2E—S1E | 123.7 (11) |
| C3B—C2B—S1B | 122.4 (3) | C3E—C2E—S1E | 121.0 (5) |
| F2B—C3B—F3B | 108.9 (5) | F2E—C3E—F3E | 109.1 (9) |
| F2B—C3B—F1B | 106.6 (5) | F2E—C3E—F1E | 107.0 (8) |
| F3B—C3B—F1B | 106.2 (5) | F3E—C3E—F1E | 105.9 (9) |
| F2B—C3B—C2B | 111.7 (4) | F2E—C3E—C2E | 113.5 (9) |
| F3B—C3B—C2B | 112.1 (4) | F3E—C3E—C2E | 110.5 (9) |
| F1B—C3B—C2B | 111.0 (4) | F1E—C3E—C2E | 110.5 (8) |
| F2B'—C3B'—F3B' | 106.6 (18) | F2E'—C3E'—F3E' | 109 (2) |
| F2B'—C3B'—F1B' | 109.8 (18) | F2E'—C3E'—F1E' | 106 (2) |
| F3B'—C3B'—F1B' | 105.5 (16) | F3E'—C3E'—F1E' | 106.1 (19) |
| F2B'—C3B'—C2B | 110.7 (16) | F2E'—C3E'—C2E | 116 (2) |
| F3B'—C3B'—C2B | 112.6 (16) | F3E'—C3E'—C2E | 111.9 (19) |
| F1B'—C3B'—C2B | 111.4 (15) | F1E'—C3E'—C2E | 107.3 (18) |
| C2C—S1C—C1C | 88.23 (8) | C2F—S1F—C1F | 88.00 (9) |
| N2C—N1C—C1C | 119.38 (15) | C1F—N1F—N2F | 119.42 (16) |
| N2C—N1C—H1C | 118.0 (16) | C1F—N1F—H1F | 120.7 (17) |
| C1C—N1C—H1C | 122.4 (16) | N2F—N1F—H1F | 119.7 (17) |
| C2C—N2C—N1C | 109.16 (15) | C2F—N2F—N1F | 109.29 (15) |
| O1C—C1C—N1C | 125.55 (17) | O1F—C1F—N1F | 126.26 (17) |
| O1C—C1C—S1C | 128.35 (14) | O1F—C1F—S1F | 127.58 (15) |
| N1C—C1C—S1C | 106.10 (12) | N1F—C1F—S1F | 106.16 (13) |
| N2C—C2C—C3C' | 118.9 (10) | N2F—C2F—C3F' | 120 (1) |
| N2C—C2C—C3C | 120.8 (3) | N2F—C2F—C3F | 120.8 (2) |
| N2C—C2C—S1C | 117.10 (14) | N2F—C2F—S1F | 117.12 (14) |
| C3C'—C2C—S1C | 123.7 (10) | C3F'—C2F—S1F | 122.7 (10) |
| C3C—C2C—S1C | 122.0 (3) | C3F—C2F—S1F | 122.07 (17) |
| F2C—C3C—F3C | 111.2 (5) | F1F—C3F—F3F | 108.5 (3) |
| F2C—C3C—F1C | 106.7 (5) | F1F—C3F—F2F | 107.2 (3) |
| F3C—C3C—F1C | 105.0 (5) | F3F—C3F—F2F | 105.7 (3) |
| F2C—C3C—C2C | 110.8 (5) | F1F—C3F—C2F | 111.7 (2) |
| F3C—C3C—C2C | 111.8 (5) | F3F—C3F—C2F | 112.0 (2) |
| F1C—C3C—C2C | 111.0 (4) | F2F—C3F—C2F | 111.4 (2) |
| F2C'—C3C'—F3C' | 101.9 (16) | F1F'—C3F'—F3F' | 97.7 (18) |
| F2C'—C3C'—F1C' | 103.9 (17) | F1F'—C3F'—F2F' | 106 (2) |
| F3C'—C3C'—F1C' | 107.0 (17) | F3F'—C3F'—F2F' | 115.2 (19) |
| F2C'—C3C'—C2C | 113.3 (17) | F1F'—C3F'—C2F | 108.7 (18) |
| F3C'—C3C'—C2C | 113.8 (17) | F3F'—C3F'—C2F | 114.3 (17) |
| F1C'—C3C'—C2C | 115.6 (16) | F2F'—C3F'—C2F | 113.6 (16) |
| C1A—N1A—N2A—C2A | 1.5 (3) | C1D—N1D—N2D—C2D | 0.5 (3) |
| N2A—N1A—C1A—O1A | 177.87 (19) | N2D—N1D—C1D—O1D | 178.44 (19) |
| N2A—N1A—C1A—S1A | −2.7 (2) | N2D—N1D—C1D—S1D | −1.0 (2) |
| C2A—S1A—C1A—O1A | −178.3 (2) | C2D—S1D—C1D—O1D | −178.59 (19) |
| C2A—S1A—C1A—N1A | 2.28 (14) | C2D—S1D—C1D—N1D | 0.85 (14) |
| N1A—N2A—C2A—C3A' | −176.0 (14) | N1D—N2D—C2D—C3D | −174.6 (9) |
| N1A—N2A—C2A—C3A | −178.6 (6) | N1D—N2D—C2D—C3D' | 176.2 (9) |
| N1A—N2A—C2A—S1A | 0.6 (2) | N1D—N2D—C2D—S1D | 0.2 (2) |
| C1A—S1A—C2A—N2A | −1.78 (17) | C1D—S1D—C2D—N2D | −0.65 (18) |
| C1A—S1A—C2A—C3A' | 174.9 (14) | C1D—S1D—C2D—C3D | 173.7 (9) |
| C1A—S1A—C2A—C3A | 177.4 (6) | C1D—S1D—C2D—C3D' | −176.8 (9) |
| N2A—C2A—C3A—F3A | 0.0 (11) | N2D—C2D—C3D—F1D | −73.1 (13) |
| S1A—C2A—C3A—F3A | −179.1 (6) | S1D—C2D—C3D—F1D | 112.6 (14) |
| N2A—C2A—C3A—F1A | −120.0 (7) | N2D—C2D—C3D—F2D | 53 (2) |
| S1A—C2A—C3A—F1A | 60.9 (10) | S1D—C2D—C3D—F2D | −121.5 (14) |
| N2A—C2A—C3A—F2A | 121.6 (7) | N2D—C2D—C3D—F3D | 167.9 (8) |
| S1A—C2A—C3A—F2A | −57.5 (10) | S1D—C2D—C3D—F3D | −6.4 (16) |
| N2A—C2A—C3A'—F3A' | −167.5 (15) | N2D—C2D—C3D'—F1D' | 106.3 (15) |
| S1A—C2A—C3A'—F3A' | 16 (3) | S1D—C2D—C3D'—F1D' | −77.8 (13) |
| N2A—C2A—C3A'—F2A' | −47 (3) | N2D—C2D—C3D'—F2D' | −128.1 (14) |
| S1A—C2A—C3A'—F2A' | 136.6 (18) | S1D—C2D—C3D'—F2D' | 48 (2) |
| N2A—C2A—C3A'—F1A' | 73 (2) | N2D—C2D—C3D'—F3D' | −13.4 (16) |
| S1A—C2A—C3A'—F1A' | −103 (2) | S1D—C2D—C3D'—F3D' | 162.4 (7) |
| C1B—N1B—N2B—C2B | 0.5 (2) | C1E—N1E—N2E—C2E | 0.9 (2) |
| N2B—N1B—C1B—O1B | 178.8 (2) | N2E—N1E—C1E—O1E | 178.64 (19) |
| N2B—N1B—C1B—S1B | −0.7 (2) | N2E—N1E—C1E—S1E | −1.6 (2) |
| C2B—S1B—C1B—O1B | −179.0 (2) | C2E—S1E—C1E—O1E | −178.87 (19) |
| C2B—S1B—C1B—N1B | 0.47 (14) | C2E—S1E—C1E—N1E | 1.36 (14) |
| N1B—N2B—C2B—C3B' | 175.6 (12) | N1E—N2E—C2E—C3E' | −178.1 (13) |
| N1B—N2B—C2B—C3B | 179.9 (3) | N1E—N2E—C2E—C3E | −177.4 (6) |
| N1B—N2B—C2B—S1B | −0.1 (2) | N1E—N2E—C2E—S1E | 0.3 (2) |
| C1B—S1B—C2B—N2B | −0.25 (16) | C1E—S1E—C2E—N2E | −1.04 (16) |
| C1B—S1B—C2B—C3B' | −176.0 (11) | C1E—S1E—C2E—C3E' | 177.3 (14) |
| C1B—S1B—C2B—C3B | 179.8 (3) | C1E—S1E—C2E—C3E | 176.7 (6) |
| N2B—C2B—C3B—F2B | −92.6 (5) | N2E—C2E—C3E—F2E | 108.4 (9) |
| S1B—C2B—C3B—F2B | 87.3 (6) | S1E—C2E—C3E—F2E | −69.2 (11) |
| N2B—C2B—C3B—F3B | 29.9 (6) | N2E—C2E—C3E—F3E | −14.5 (13) |
| S1B—C2B—C3B—F3B | −150.1 (4) | S1E—C2E—C3E—F3E | 167.9 (8) |
| N2B—C2B—C3B—F1B | 148.5 (4) | N2E—C2E—C3E—F1E | −131.3 (8) |
| S1B—C2B—C3B—F1B | −31.5 (6) | S1E—C2E—C3E—F1E | 51.0 (12) |
| N2B—C2B—C3B'—F2B' | 105.9 (18) | N2E—C2E—C3E'—F2E' | −29 (3) |
| S1B—C2B—C3B'—F2B' | −79 (2) | S1E—C2E—C3E'—F2E' | 152.8 (17) |
| N2B—C2B—C3B'—F3B' | −134.9 (15) | N2E—C2E—C3E'—F3E' | −155 (2) |
| S1B—C2B—C3B'—F3B' | 41 (2) | S1E—C2E—C3E'—F3E' | 27 (3) |
| N2B—C2B—C3B'—F1B' | −17 (2) | N2E—C2E—C3E'—F1E' | 89 (2) |
| S1B—C2B—C3B'—F1B' | 158.9 (14) | S1E—C2E—C3E'—F1E' | −89 (2) |
| C1C—N1C—N2C—C2C | 0.7 (3) | C1F—N1F—N2F—C2F | −0.9 (3) |
| N2C—N1C—C1C—O1C | 179.06 (19) | N2F—N1F—C1F—O1F | −179.47 (19) |
| N2C—N1C—C1C—S1C | −1.6 (2) | N2F—N1F—C1F—S1F | 1.2 (2) |
| C2C—S1C—C1C—O1C | −179.2 (2) | C2F—S1F—C1F—O1F | 179.82 (19) |
| C2C—S1C—C1C—N1C | 1.48 (14) | C2F—S1F—C1F—N1F | −0.88 (14) |
| N1C—N2C—C2C—C3C' | −173.3 (12) | N1F—N2F—C2F—C3F' | −174.3 (13) |
| N1C—N2C—C2C—C3C | −177.6 (4) | N1F—N2F—C2F—C3F | −178.5 (2) |
| N1C—N2C—C2C—S1C | 0.6 (2) | N1F—N2F—C2F—S1F | 0.1 (2) |
| C1C—S1C—C2C—N2C | −1.29 (17) | C1F—S1F—C2F—N2F | 0.50 (17) |
| C1C—S1C—C2C—C3C' | 172.3 (12) | C1F—S1F—C2F—C3F' | 174.7 (13) |
| C1C—S1C—C2C—C3C | 176.9 (4) | C1F—S1F—C2F—C3F | 179.1 (2) |
| N2C—C2C—C3C—F2C | 105.1 (6) | N2F—C2F—C3F—F1F | 92.2 (3) |
| S1C—C2C—C3C—F2C | −73.0 (6) | S1F—C2F—C3F—F1F | −86.3 (3) |
| N2C—C2C—C3C—F3C | −19.6 (7) | N2F—C2F—C3F—F3F | −29.7 (4) |
| S1C—C2C—C3C—F3C | 162.2 (4) | S1F—C2F—C3F—F3F | 151.8 (2) |
| N2C—C2C—C3C—F1C | −136.5 (4) | N2F—C2F—C3F—F2F | −147.8 (2) |
| S1C—C2C—C3C—F1C | 45.4 (7) | S1F—C2F—C3F—F2F | 33.6 (3) |
| N2C—C2C—C3C'—F2C' | −82 (2) | N2F—C2F—C3F'—F1F' | −98.9 (19) |
| S1C—C2C—C3C'—F2C' | 104.1 (19) | S1F—C2F—C3F'—F1F' | 87 (2) |
| N2C—C2C—C3C'—F3C' | 161.8 (15) | N2F—C2F—C3F'—F3F' | 153.2 (17) |
| S1C—C2C—C3C'—F3C' | −12 (3) | S1F—C2F—C3F'—F3F' | −21 (3) |
| N2C—C2C—C3C'—F1C' | 37 (2) | N2F—C2F—C3F'—F2F' | 18 (3) |
| S1C—C2C—C3C'—F1C' | −136.1 (15) | S1F—C2F—C3F'—F2F' | −155.7 (15) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1A—H1A···O1B | 0.82 (2) | 1.92 (2) | 2.726 (2) | 169 (2) |
| N1B—H1B···O1A | 0.83 (2) | 2.57 (2) | 3.328 (2) | 152 (2) |
| N1B—H1B···O1Ai | 0.83 (2) | 2.35 (2) | 2.955 (2) | 131 (2) |
| N1C—H1C···O1D | 0.83 (2) | 1.93 (2) | 2.7485 (19) | 171 (2) |
| N1D—H1D···O1C | 0.82 (2) | 2.61 (2) | 3.342 (2) | 150 (2) |
| N1D—H1D···O1F | 0.82 (2) | 2.28 (2) | 2.908 (2) | 134 (2) |
| N1E—H1E···O1C | 0.81 (2) | 2.26 (2) | 2.912 (2) | 137 (2) |
| N1E—H1E···O1F | 0.81 (2) | 2.64 (2) | 3.359 (2) | 148 (2) |
| N1F—H1F···O1E | 0.82 (2) | 1.95 (2) | 2.764 (2) | 171 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1.
Funding Statement
Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (award No. CHE-1625732 to SP).
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023004267/vm2283sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023004267/vm2283Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989023004267/vm2283Isup3.cml
CCDC reference: 2263179
Additional supporting information: crystallographic information; 3D view; checkCIF report