research communications
Synthesis and H)-one at 180 K
studies of 5-(trifluoromethyl)-1,3,4-thiadiazol-2(3aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, bDepartment of Chemistry, Amrita School of Engineering, Amrita Vishwa Vidyapeetham, Bengaluru-560 035, India, cDepartment of Science and Humanities, PES University, BSK III Stage, Bengaluru-560 085, India, dHoneychem Pharma Research Pvt. Ltd., Peenya Industrial Area, Bengaluru-560 058, India, and eDepartment of Chemistry, University of Kentucky, Lexington, KY, 40506-0055, USA
*Correspondence e-mail: ybb2706@gmail.com, yathirajan@hotmail.com
The synthesis and 3HF3N2OS, 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 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.
of CKeywords: 1,3,4-thiadiazole; heterocycle; high Z′; Z′ = 6; hydrogen bonding; disorder; crystal structure.
CCDC reference: 2263179
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 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 H)-one, C3HF3N2OS (5-TMD-2-one).
of 5-(trifluoromethyl)-1,3,4-thiadiazol-2(32. 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 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.
of 5-TMD-2-one is far more complex, as the contains six molecules (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 i.e., with fewer molecules in the A crystal mounted at room temperature, however, indexed to give essentially the same 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 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 R22(8) dimer motifs. Pairs of these dimers are connected to inversion-related copies by N1B—H1B⋯O1Ai [dD–A = 2.955 (2) Å; symmetry code: (i) 2 − x, 1 − y, 1 − z] hydrogen bonds, producing R22(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⋯O1Bii = 2.9743 (14) Å and O1B⋯O1Bii = 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 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.
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. 4a–f). The most abundant contacts in each case are F⋯F (shown in blue and green), ranging from 39.8% in molecule A (Fig. 4a) to 25.6% in molecule E (Fig. 4e).
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 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)+.
6. Refinement
Crystal data, data collection and structure . All hydrogen atoms were found in difference-Fourier maps. Their coordinates were refined freely with Uiso parameters set to 1.2Ueq of their attached nitrogen atom. To ensure satisfactory of the disordered CF3 groups, a combination of constraints (EADP in SHELXL) and restraints (SHELXL commands SAME, SADI, SIMU, and RIGU) were employed.
details are summarized in Table 2
|
Supporting information
CCDC reference: 2263179
https://doi.org/10.1107/S2056989023004267/vm2283sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004267/vm2283Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023004267/vm2283Isup3.cml
Data collection: APEX3 (Bruker, 2016); cell
APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELX (Sheldrick, 2008) and publCIF (Westrip, 2010).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 |
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 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) |
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. |
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) |
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) |
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) |
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. |
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—O1Ai | 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—H1EE—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···O1Bii | 2.9743 (14) | |||
O1B···O1Bii | 2.996 (3) | |||
S1D···O1Eiii | 3.0279 (14) | |||
O1D···O1Eiii | 3.0686 (18) | |||
O1D···S1Eiii | 3.0093 (14) |
Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z + 1; (iii) x - 1, y, z. |
Acknowledgements
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.
Funding information
Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (award No. CHE-1625732 to SP).
References
Anthwal, T., Paliwal, S. & Nain, S. (2022). Chemistry, 4, 1654–1671. CrossRef CAS Google Scholar
Barbosa, G. A. D. & de Aguiar, A. P. (2019). Rev. Virtual Quim., 11, 806–848. Google Scholar
Boechat, N., Ferreira, S. B., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, S. M. S. V. (2006). Acta Cryst. C62, o42–o44. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Brock, C. P. (2016). Acta Cryst. B72, 807–821. Web of Science CrossRef IUCr Journals Google Scholar
Bruker (2016). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Çevik, U. A., Osmaniye, D., Levent, S., Sağlik, B. N., Çavuşoğlu, B. K., Özkay, Y. & Kaplancikl, Z. A. (2020). Heterocycl. Commun. 26, 6–13. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Han, X., Yu, Y. L., Hu, Y. S. & Liu, X. H. (2021). Curr. Top. Med. Chem. 21, 2546–2573. CrossRef CAS PubMed Google Scholar
Hartung, R., Golz, G., Schlaf, S., Silvenoinen, G., Polborn, K., Mayer, P. & Pfaendler, H. R. (2009). Synthesis, pp. 495–501. Google Scholar
Hoser, A. A., Kamiński, D. M., Skrzypek, A., Matwijczuk, A., Niewiadomy, A., Gagoś, M. & Woźniak, K. (2018). Cryst. Growth Des. 18, 3851–3862. CSD CrossRef CAS Google Scholar
Hu, P.-Z., Wang, J.-G., Ma, L.-F., Zhao, B.-T. & Wang, L.-Y. (2006). Acta Cryst. E62, o350–o351. CSD CrossRef IUCr Journals Google Scholar
Jain, A. K., Sharma, S., Vaidya, A., Ravichandran, V. & Agrawal, R. K. (2013). Chem. Biol. Drug Des. 81, 557–576. Web of Science CrossRef CAS PubMed Google Scholar
Kang, S. K., Cho, N. S. & Jang, S. (2012a). Acta Cryst. E68, o781. CSD CrossRef IUCr Journals Google Scholar
Kang, S. K., Cho, N. S. & Jang, S. (2012b). Acta Cryst. E68, o1198. CSD CrossRef IUCr Journals Google Scholar
Kim, N. & Kang, S. K. (2014). Acta Cryst. E70, o922. CSD CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Moussa, Z., Paz, A. P., Judeh, Z. M. A., Alzamly, A., Saadeh, H. A., Asghar, B. H., Alsaedi, S., Masoud, B., Almeqbaali, S., Estwani, S., Aljaberi, A., Al-Rooqi, M. M. & Ahmed, S. A. (2023). Int. J. Mol. Sci. 24, 3759. CrossRef PubMed Google Scholar
Oruç, E. E., Rollas, S., Kandemirli, F., Shvets, N. & Dimoglo, A. S. (2004). J. Med. Chem. 47, 6760–6767. Web of Science PubMed Google Scholar
Panini, P., Mohan, T. P., Gangwar, U., Sankolli, R. & Chopra, D. (2013). CrystEngComm, 15, 4549–4564. Web of Science CSD CrossRef CAS Google Scholar
Serban, G., Stanasel, O., Serban, E. & Bota, S. (2018). Drug. Des. Dev. Ther. Vol. 12, 1545–1566. CrossRef CAS Google Scholar
Shamanth, S., Mantelingu, K., Kiran Kumar, H., Yathirajan, H. S., Foro, S. & Glidewell, C. (2020). Acta Cryst. E76, 18–24. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shen, X.-Q., Li, Z.-J., Zhang, H.-Y., Qiao, H.-B., Wu, Q.-A., Wang, H.-Y. & Zu, Y. (2005). J. Phys. Chem. Solids, 66, 1755–1760. CSD CrossRef CAS Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, W.-Y., Liu, J. & Liu, Y.-J. (2012). Acta Cryst. E68, o475. CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.