organic compounds
(2E)-N-Methyl-2-[1-(4-methylcyclohex-3-en-1-yl)ethylidene]hydrazinecarbothioamide
aLaboratory of Organic Synthesis and Physico-Molecular Chemistry, Department of Chemistry, Faculty, Sciences Semlalia, BP 2390, Marrakech 40001, Morocco, bInstitute of Molecular Chemistry of Reims, CNRS UMR 7312 Bat. Europol'Agro, Moulin of the Housse UFR Sciences, BP 1039-51687 Reims Cedex 2, France, and cLaboratory of Applied Spectro-Chemistry and Environment, University Sultan Moulay Slimane, Faculty of Science and Technology, PO Box 523, Beni-Mellal, Morocco
*Correspondence e-mail: elm_ketatni@hotmail.fr
There are two independent molecules (A and B) in the of the title compound, C11H19N3S. In molecule B, two C atoms and the associated H atoms of the cyclohexene ring are disordered over two sets of sites with a site occupancy ratio of 0.649 (7):0.351 (7). The N—N—C—N fragments of the hydrazinecarbothioamide segments of both molecules are not planar, with a torsion angle of −5.8 (3)° for A and 11.6 (3)° for B. The stability of the conformations of both molecules is aided by the formation of intramolecular N—H⋯N hydrogen bonds. In the crystal, N—H⋯S hydrogen bonds link like molecules into R22(8) A + B dimers. These dimers are interconnected by additional N—H⋯S contacts, forming chains along the c-axis direction. The structure was refined as a two-component inversion twin.
Keywords: crystal structure; hydrazinecarbothiamide; natural product; hydrogen bond.
CCDC reference: 1541850
Structure description
Thiosemicarbazones are a class of molecules that have been investigated over the last 50 years as antiviral (Pirrung et al. 2005) and antitumor agents (Hu et al. 2006). In addition, they show antiparasitic and antibacterial action against Trypanasoma cruzi (Du et al. 2002) and Toxoplasma gondii and against several other bacterial strains (de Aquino et al. 2008). To further our work on new thiosemicarbazone derivatives, we have prepared the title compound by the reaction of 4-acetyl-1-methylcyclohexene, a natural product extracted from the essential oil of Cedrus atlanica (Grimal, 1902), with 4-methyl-3-thiosemicarbazide in ethanol.
The title compound, crystallizes with two independent molecules (A and B) in the (Fig. 1). The N3—N2—C2—N1 and N6—N5—C13 fragments are not planar with torsion angles −5.8 (3) and 11.6 (3), respectively in molecules A and B. In each hydrazinecarbothioamide unit (=N—NH—C(=S)—NH–), the N—H hydrogen atoms are anti, and the terminal N—H hydrogen atoms form intramolecular N1—H1N⋯N3 and N4—H4N⋯N6 hydrogen bonds with S(5) ring motifs (Fig. 1 and Table 1). The bond lengths and angles of the title compound are normal and agree with those values reported in other methyl-hydrazinecarbothioamide structures (Gangadharan et al., 2015; de Oliveira et al., 2017; Tayamon et al., 2012). In both molecules, the thiosemicarbazone groups adopts an extended conformation, as shown by the torsion angles S1—C2—N2—N3 [175.83 (14)°, molecule A] and S2—C13—N5—N6 [−171.21 (15)°, molecule B].
In the crystal, the two independent molecules are linked by a pair of (N2, N5)—H⋯S hydrogen bonds, Table 1, forming A–B dimers with R22(8) ring motifs. These dimers are linked by N4—H⋯S hydrogen bonds, forming chains along the c-axis direction. Adjacent chains form sheets parallel to (001), Figs. 2 and 3.
Synthesis and crystallization
To a solution of 4-methyl-3-thiosemicarbazide (1.43 g, 13.61 mmol) in ethanol (72 ml) was added 4-acetyl-1-methylcyclohexene (2 g, 14.29 mmol) and acetic acid (0.50 ml). The mixture was stirred at 85°C for 3 h. After cooling, the mixture was extracted with dichloromethane (3× 20 ml). The combined organic layers were washed with water, dried over anhydrous Na2SO4 and then evaporated under reduced pressure. The residue was chromatographed on a silica gel column using hexane/ethyl acetate (92/8) as to give the title compound (2.286 g) in 88% yield. Colourless plate-like crystals were obtained from a petroleum ether solution, by slow evaporation of the solvent at room temperature.
Refinement
Crystal data, data collection and structure . The structure was refined as a two-component The C15 and C16 atoms of the cyclohexene ring in molecule B and their associated hydrogen atoms are disordered over two sets of sites with refined site occupancies of 0.649 (7) and 0.351 (7). This disorder inverts the configuration at C15 (R for C15 and S for C15A). The configuration at C4 in molecule A is R.
details are summarized in Table 2
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Structural data
CCDC reference: 1541850
https://doi.org/10.1107/S2414314617005132/sj4102sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005132/sj4102Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617005132/sj4102Isup3.cml
Data collection: APEX2 (Bruker,2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg et al., 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).C11H19N3S | Dx = 1.190 Mg m−3 |
Mr = 225.35 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 5139 reflections |
a = 12.2974 (4) Å | θ = 4.4–74.6° |
b = 13.7295 (4) Å | µ = 2.07 mm−1 |
c = 14.8952 (5) Å | T = 100 K |
V = 2514.86 (14) Å3 | Plate, colourless |
Z = 8 | 0.44 × 0.31 × 0.22 mm |
F(000) = 976 |
Bruker D8 venture CMOS area-detector diffractometer | 5028 reflections with I > 2σ(I) |
Radiation source: microsource | Rint = 0.035 |
φ and ω scans | θmax = 74.6°, θmin = 4.4° |
Absorption correction: numerical (SADABS; Bruker, 2012) | h = −15→15 |
Tmin = 0.707, Tmax = 0.858 | k = −17→17 |
48702 measured reflections | l = −18→18 |
5139 independent reflections |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0308P)2 + 0.9302P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.070 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.22 e Å−3 |
5139 reflections | Δρmin = −0.31 e Å−3 |
319 parameters | Absolute structure: Refined as an inversion twin |
0 restraints | Absolute structure parameter: 0.065 (15) |
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. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.36364 (4) | 0.94045 (4) | 0.01514 (3) | 0.02417 (12) | |
N1 | 0.49945 (15) | 0.82337 (14) | 0.10431 (12) | 0.0243 (4) | |
H1N | 0.530 (2) | 0.767 (2) | 0.1124 (19) | 0.033 (7)* | |
N2 | 0.39334 (15) | 0.75188 (13) | −0.00369 (12) | 0.0240 (4) | |
H2N | 0.347 (2) | 0.757 (2) | −0.0494 (19) | 0.033 (7)* | |
N3 | 0.44757 (15) | 0.66492 (12) | 0.01283 (12) | 0.0222 (3) | |
C1 | 0.53214 (19) | 0.90195 (17) | 0.16325 (16) | 0.0295 (5) | |
H1A | 0.5535 | 0.9573 | 0.1280 | 0.044* | |
H1B | 0.5923 | 0.8811 | 0.1996 | 0.044* | |
H1C | 0.4723 | 0.9196 | 0.2013 | 0.044* | |
C2 | 0.42426 (17) | 0.83324 (15) | 0.04084 (13) | 0.0204 (4) | |
C3 | 0.40645 (18) | 0.58777 (15) | −0.02091 (14) | 0.0247 (4) | |
C4 | 0.46798 (17) | 0.49360 (14) | −0.01048 (14) | 0.0223 (4) | |
H4 | 0.4165 | 0.4450 | 0.0123 | 0.027* | |
C5 | 0.5621 (2) | 0.49720 (16) | 0.05467 (16) | 0.0305 (5) | |
H5A | 0.6164 | 0.5430 | 0.0334 | 0.037* | |
H5B | 0.5367 | 0.5190 | 0.1130 | 0.037* | |
C6 | 0.6116 (3) | 0.3972 (2) | 0.0628 (2) | 0.0671 (12) | |
H6A | 0.6843 | 0.4050 | 0.0872 | 0.081* | |
H6B | 0.5697 | 0.3614 | 0.1070 | 0.081* | |
C7 | 0.62018 (19) | 0.33763 (16) | −0.01496 (19) | 0.0346 (5) | |
C8 | 0.5671 (3) | 0.3628 (2) | −0.0924 (2) | 0.0592 (9) | |
H8 | 0.5676 | 0.3198 | −0.1406 | 0.071* | |
C9 | 0.5082 (2) | 0.45746 (18) | −0.10149 (15) | 0.0343 (5) | |
H9A | 0.4468 | 0.4493 | −0.1416 | 0.041* | |
H9B | 0.5565 | 0.5056 | −0.1276 | 0.041* | |
C10 | 0.6836 (2) | 0.24421 (19) | −0.0102 (3) | 0.0538 (8) | |
H10A | 0.6423 | 0.1964 | 0.0223 | 0.081* | |
H10B | 0.7513 | 0.2556 | 0.0201 | 0.081* | |
H10C | 0.6975 | 0.2209 | −0.0698 | 0.081* | |
C11 | 0.3008 (2) | 0.58335 (17) | −0.07200 (18) | 0.0373 (6) | |
H11A | 0.2498 | 0.6280 | −0.0459 | 0.056* | |
H11B | 0.2720 | 0.5184 | −0.0691 | 0.056* | |
H11C | 0.3134 | 0.6008 | −0.1335 | 0.056* | |
S2 | 0.76273 (5) | 0.27916 (4) | 0.69275 (3) | 0.02686 (13) | |
N4 | 0.83663 (15) | 0.40843 (15) | 0.81084 (14) | 0.0285 (4) | |
H4N | 0.830 (2) | 0.465 (2) | 0.836 (2) | 0.036 (8)* | |
N5 | 0.70352 (17) | 0.46203 (13) | 0.71559 (12) | 0.0259 (4) | |
H5N | 0.671 (2) | 0.453 (2) | 0.665 (2) | 0.033 (7)* | |
N6 | 0.72110 (17) | 0.55541 (14) | 0.74845 (13) | 0.0316 (4) | |
C12 | 0.9124 (2) | 0.3382 (2) | 0.84744 (17) | 0.0358 (6) | |
H12A | 0.8746 | 0.2788 | 0.8610 | 0.054* | |
H12B | 0.9442 | 0.3638 | 0.9013 | 0.054* | |
H12C | 0.9686 | 0.3253 | 0.8043 | 0.054* | |
C13 | 0.77058 (18) | 0.38938 (15) | 0.74270 (13) | 0.0239 (4) | |
C14 | 0.6501 (3) | 0.62087 (16) | 0.72682 (18) | 0.0393 (7) | |
C18 | 0.70439 (19) | 0.91269 (15) | 0.82868 (14) | 0.0269 (5) | |
C17 | 0.7888 (2) | 0.8686 (2) | 0.7702 (2) | 0.0425 (6) | |
H17A | 0.866 (3) | 0.875 (2) | 0.798 (2) | 0.051* | |
H17B | 0.801 (3) | 0.899 (2) | 0.706 (2) | 0.051* | |
C19 | 0.6175 (2) | 0.86244 (16) | 0.85558 (16) | 0.0337 (6) | |
H19 | 0.5679 | 0.8934 | 0.8930 | 0.040* | |
C20 | 0.5949 (2) | 0.75825 (16) | 0.82896 (17) | 0.0335 (5) | |
H20A | 0.5180 | 0.7512 | 0.8159 | 0.040* | |
H20B | 0.6122 | 0.7158 | 0.8790 | 0.040* | |
C21 | 0.7221 (2) | 1.01765 (16) | 0.85489 (17) | 0.0374 (6) | |
H21A | 0.7109 | 1.0587 | 0.8035 | 0.056* | |
H21B | 0.7951 | 1.0258 | 0.8765 | 0.056* | |
H21C | 0.6717 | 1.0352 | 0.9013 | 0.056* | |
C22 | 0.5491 (3) | 0.6021 (2) | 0.6742 (2) | 0.0578 (9) | |
H22A | 0.5153 | 0.5434 | 0.6954 | 0.087* | |
H22B | 0.5671 | 0.5950 | 0.6118 | 0.087* | |
H22C | 0.4998 | 0.6557 | 0.6815 | 0.087* | |
C15 | 0.6606 (3) | 0.7265 (3) | 0.7470 (3) | 0.0198 (8) | 0.649 (7) |
H15 | 0.6371 | 0.7642 | 0.6947 | 0.024* | 0.649 (7) |
C16 | 0.7785 (3) | 0.7517 (2) | 0.7685 (2) | 0.0256 (10) | 0.649 (7) |
H16A | 0.8265 | 0.7247 | 0.7232 | 0.031* | 0.649 (7) |
H16B | 0.7988 | 0.7248 | 0.8264 | 0.031* | 0.649 (7) |
C16A | 0.7427 (5) | 0.7894 (4) | 0.7130 (4) | 0.0218 (17) | 0.351 (7) |
H'A | 0.7982 | 0.7606 | 0.6751 | 0.026* | 0.351 (7) |
H'B | 0.6840 | 0.8135 | 0.6756 | 0.026* | 0.351 (7) |
C15A | 0.7013 (6) | 0.7169 (5) | 0.7815 (5) | 0.0185 (15) | 0.351 (7) |
H15A | 0.7575 | 0.6982 | 0.8249 | 0.022* | 0.351 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0334 (3) | 0.0203 (2) | 0.0188 (2) | 0.0051 (2) | −0.0011 (2) | −0.00187 (19) |
N1 | 0.0287 (9) | 0.0191 (8) | 0.0252 (9) | 0.0017 (8) | −0.0034 (7) | −0.0026 (7) |
N2 | 0.0341 (9) | 0.0185 (8) | 0.0194 (8) | −0.0007 (7) | −0.0047 (7) | 0.0009 (6) |
N3 | 0.0318 (9) | 0.0177 (8) | 0.0170 (8) | 0.0001 (7) | −0.0006 (7) | 0.0012 (7) |
C1 | 0.0286 (11) | 0.0268 (11) | 0.0330 (12) | 0.0035 (9) | −0.0089 (9) | −0.0089 (9) |
C2 | 0.0247 (10) | 0.0200 (10) | 0.0165 (9) | −0.0022 (8) | 0.0036 (7) | 0.0001 (7) |
C3 | 0.0363 (11) | 0.0202 (10) | 0.0176 (9) | −0.0056 (8) | −0.0016 (9) | 0.0028 (8) |
C4 | 0.0313 (10) | 0.0178 (9) | 0.0179 (9) | −0.0047 (8) | 0.0019 (8) | 0.0000 (8) |
C5 | 0.0447 (13) | 0.0201 (11) | 0.0266 (11) | 0.0050 (10) | −0.0094 (10) | −0.0067 (9) |
C6 | 0.101 (3) | 0.0338 (15) | 0.067 (2) | 0.0305 (17) | −0.052 (2) | −0.0223 (15) |
C7 | 0.0301 (11) | 0.0220 (10) | 0.0517 (14) | −0.0044 (9) | 0.0095 (11) | −0.0124 (10) |
C8 | 0.082 (2) | 0.060 (2) | 0.0355 (15) | 0.0271 (18) | −0.0011 (15) | −0.0265 (14) |
C9 | 0.0521 (15) | 0.0318 (12) | 0.0188 (10) | −0.0099 (11) | 0.0037 (10) | −0.0058 (9) |
C10 | 0.0443 (15) | 0.0275 (12) | 0.090 (2) | 0.0040 (11) | 0.0063 (16) | −0.0202 (15) |
C11 | 0.0498 (15) | 0.0215 (11) | 0.0405 (13) | −0.0062 (10) | −0.0178 (12) | 0.0050 (9) |
S2 | 0.0371 (3) | 0.0182 (2) | 0.0252 (2) | 0.0030 (2) | −0.0074 (2) | −0.00647 (19) |
N4 | 0.0272 (9) | 0.0307 (10) | 0.0276 (9) | −0.0047 (7) | 0.0000 (8) | −0.0112 (8) |
N5 | 0.0408 (11) | 0.0149 (8) | 0.0220 (9) | −0.0015 (7) | −0.0006 (8) | −0.0059 (7) |
N6 | 0.0428 (11) | 0.0209 (9) | 0.0312 (10) | −0.0111 (8) | 0.0174 (9) | −0.0126 (8) |
C12 | 0.0275 (11) | 0.0466 (15) | 0.0332 (13) | −0.0005 (10) | −0.0069 (10) | −0.0100 (11) |
C13 | 0.0294 (10) | 0.0224 (10) | 0.0199 (9) | −0.0048 (9) | 0.0045 (8) | −0.0032 (8) |
C14 | 0.0651 (18) | 0.0145 (10) | 0.0384 (13) | −0.0008 (11) | 0.0292 (13) | −0.0041 (9) |
C18 | 0.0380 (12) | 0.0208 (10) | 0.0218 (10) | 0.0014 (9) | −0.0067 (9) | −0.0012 (8) |
C17 | 0.0307 (13) | 0.0388 (14) | 0.0581 (17) | −0.0103 (10) | 0.0025 (12) | −0.0212 (13) |
C19 | 0.0527 (16) | 0.0177 (10) | 0.0308 (12) | 0.0059 (10) | 0.0164 (11) | −0.0023 (9) |
C20 | 0.0442 (13) | 0.0188 (10) | 0.0376 (13) | −0.0006 (9) | 0.0204 (11) | −0.0027 (9) |
C21 | 0.0553 (16) | 0.0204 (11) | 0.0365 (13) | −0.0005 (11) | −0.0114 (12) | −0.0020 (9) |
C22 | 0.101 (3) | 0.0314 (14) | 0.0406 (16) | 0.0296 (16) | −0.0126 (16) | −0.0069 (12) |
C15 | 0.0216 (19) | 0.0175 (17) | 0.0203 (19) | −0.0014 (14) | −0.0027 (15) | −0.0021 (14) |
C16 | 0.0243 (18) | 0.0187 (16) | 0.034 (2) | 0.0019 (13) | −0.0032 (15) | −0.0033 (14) |
C16A | 0.024 (3) | 0.019 (3) | 0.022 (3) | 0.003 (2) | 0.000 (2) | 0.000 (2) |
C15A | 0.024 (4) | 0.011 (3) | 0.020 (3) | −0.002 (3) | 0.001 (3) | −0.006 (2) |
S1—C2 | 1.694 (2) | N5—C13 | 1.356 (3) |
N1—C2 | 1.329 (3) | N5—N6 | 1.389 (2) |
N1—C1 | 1.448 (3) | N5—H5N | 0.86 (3) |
N1—H1N | 0.87 (3) | N6—C14 | 1.294 (4) |
N2—C2 | 1.354 (3) | C12—H12A | 0.9600 |
N2—N3 | 1.389 (2) | C12—H12B | 0.9600 |
N2—H2N | 0.89 (3) | C12—H12C | 0.9600 |
N3—C3 | 1.277 (3) | C14—C15 | 1.487 (4) |
C1—H1A | 0.9600 | C14—C22 | 1.492 (5) |
C1—H1B | 0.9600 | C14—C15A | 1.673 (7) |
C1—H1C | 0.9600 | C18—C19 | 1.333 (4) |
C3—C4 | 1.506 (3) | C18—C17 | 1.484 (4) |
C3—C11 | 1.507 (3) | C18—C21 | 1.509 (3) |
C4—C5 | 1.511 (3) | C17—C16A | 1.494 (6) |
C4—C9 | 1.526 (3) | C17—C16 | 1.610 (4) |
C4—H4 | 0.9800 | C17—H17A | 1.04 (3) |
C5—C6 | 1.507 (3) | C17—H17B | 1.06 (3) |
C5—H5A | 0.9700 | C19—C20 | 1.510 (3) |
C5—H5B | 0.9700 | C19—H19 | 0.9300 |
C6—C7 | 1.422 (4) | C20—C15 | 1.527 (4) |
C6—H6A | 0.9700 | C20—C15A | 1.592 (7) |
C6—H6B | 0.9700 | C20—H20A | 0.9700 |
C7—C8 | 1.370 (4) | C20—H20B | 0.9700 |
C7—C10 | 1.503 (3) | C21—H21A | 0.9600 |
C8—C9 | 1.493 (4) | C21—H21B | 0.9600 |
C8—H8 | 0.9300 | C21—H21C | 0.9600 |
C9—H9A | 0.9700 | C22—H22A | 0.9600 |
C9—H9B | 0.9700 | C22—H22B | 0.9600 |
C10—H10A | 0.9600 | C22—H22C | 0.9600 |
C10—H10B | 0.9600 | C15—C16 | 1.524 (5) |
C10—H10C | 0.9600 | C15—H15 | 0.9800 |
C11—H11A | 0.9600 | C16—H16A | 0.9700 |
C11—H11B | 0.9600 | C16—H16B | 0.9700 |
C11—H11C | 0.9600 | C16A—C15A | 1.513 (9) |
S2—C13 | 1.689 (2) | C16A—H'A | 0.9700 |
N4—C13 | 1.326 (3) | C16A—H'B | 0.9700 |
N4—C12 | 1.447 (3) | C15A—H15A | 0.9800 |
N4—H4N | 0.87 (3) | ||
C2—N1—C1 | 123.25 (19) | H12A—C12—H12B | 109.5 |
C2—N1—H1N | 119.5 (19) | N4—C12—H12C | 109.5 |
C1—N1—H1N | 117.3 (19) | H12A—C12—H12C | 109.5 |
C2—N2—N3 | 119.18 (18) | H12B—C12—H12C | 109.5 |
C2—N2—H2N | 119.0 (18) | N4—C13—N5 | 117.09 (19) |
N3—N2—H2N | 121.0 (18) | N4—C13—S2 | 123.30 (18) |
C3—N3—N2 | 116.94 (18) | N5—C13—S2 | 119.55 (16) |
N1—C1—H1A | 109.5 | N6—C14—C15 | 124.7 (3) |
N1—C1—H1B | 109.5 | N6—C14—C22 | 124.9 (2) |
H1A—C1—H1B | 109.5 | C15—C14—C22 | 110.3 (3) |
N1—C1—H1C | 109.5 | N6—C14—C15A | 99.9 (4) |
H1A—C1—H1C | 109.5 | C22—C14—C15A | 134.9 (4) |
H1B—C1—H1C | 109.5 | C19—C18—C17 | 121.7 (2) |
N1—C2—N2 | 117.37 (19) | C19—C18—C21 | 122.2 (2) |
N1—C2—S1 | 123.74 (16) | C17—C18—C21 | 116.1 (2) |
N2—C2—S1 | 118.87 (16) | C18—C17—C16A | 111.5 (3) |
N3—C3—C4 | 118.21 (19) | C18—C17—C16 | 111.2 (2) |
N3—C3—C11 | 125.0 (2) | C18—C17—H17A | 111.6 (18) |
C4—C3—C11 | 116.79 (18) | C16A—C17—H17A | 129.7 (18) |
C3—C4—C5 | 115.02 (17) | C16—C17—H17A | 99.6 (18) |
C3—C4—C9 | 110.51 (18) | C18—C17—H17B | 118.1 (18) |
C5—C4—C9 | 109.44 (19) | C16A—C17—H17B | 80.1 (18) |
C3—C4—H4 | 107.2 | C16—C17—H17B | 113.2 (18) |
C5—C4—H4 | 107.2 | H17A—C17—H17B | 101 (3) |
C9—C4—H4 | 107.2 | C18—C19—C20 | 124.0 (2) |
C6—C5—C4 | 109.36 (19) | C18—C19—H19 | 118.0 |
C6—C5—H5A | 109.8 | C20—C19—H19 | 118.0 |
C4—C5—H5A | 109.8 | C19—C20—C15 | 112.5 (2) |
C6—C5—H5B | 109.8 | C19—C20—C15A | 107.6 (3) |
C4—C5—H5B | 109.8 | C19—C20—H20A | 109.1 |
H5A—C5—H5B | 108.3 | C15—C20—H20A | 109.1 |
C7—C6—C5 | 119.2 (3) | C19—C20—H20B | 109.1 |
C7—C6—H6A | 107.5 | C15—C20—H20B | 109.1 |
C5—C6—H6A | 107.5 | H20A—C20—H20B | 107.8 |
C7—C6—H6B | 107.5 | C18—C21—H21A | 109.5 |
C5—C6—H6B | 107.5 | C18—C21—H21B | 109.5 |
H6A—C6—H6B | 107.0 | H21A—C21—H21B | 109.5 |
C8—C7—C6 | 120.4 (2) | C18—C21—H21C | 109.5 |
C8—C7—C10 | 120.2 (3) | H21A—C21—H21C | 109.5 |
C6—C7—C10 | 119.4 (3) | H21B—C21—H21C | 109.5 |
C7—C8—C9 | 121.8 (2) | C14—C22—H22A | 109.5 |
C7—C8—H8 | 119.1 | C14—C22—H22B | 109.5 |
C9—C8—H8 | 119.1 | H22A—C22—H22B | 109.5 |
C8—C9—C4 | 111.0 (2) | C14—C22—H22C | 109.5 |
C8—C9—H9A | 109.4 | H22A—C22—H22C | 109.5 |
C4—C9—H9A | 109.4 | H22B—C22—H22C | 109.5 |
C8—C9—H9B | 109.4 | C14—C15—C16 | 110.3 (3) |
C4—C9—H9B | 109.4 | C14—C15—C20 | 113.2 (3) |
H9A—C9—H9B | 108.0 | C16—C15—C20 | 105.7 (3) |
C7—C10—H10A | 109.5 | C14—C15—H15 | 109.2 |
C7—C10—H10B | 109.5 | C16—C15—H15 | 109.2 |
H10A—C10—H10B | 109.5 | C20—C15—H15 | 109.2 |
C7—C10—H10C | 109.5 | C15—C16—C17 | 107.7 (3) |
H10A—C10—H10C | 109.5 | C15—C16—H16A | 110.2 |
H10B—C10—H10C | 109.5 | C17—C16—H16A | 110.2 |
C3—C11—H11A | 109.5 | C15—C16—H16B | 110.2 |
C3—C11—H11B | 109.5 | C17—C16—H16B | 110.2 |
H11A—C11—H11B | 109.5 | H16A—C16—H16B | 108.5 |
C3—C11—H11C | 109.5 | C17—C16A—C15A | 102.8 (5) |
H11A—C11—H11C | 109.5 | C17—C16A—H'A | 111.2 |
H11B—C11—H11C | 109.5 | C15A—C16A—H'A | 111.2 |
C13—N4—C12 | 123.4 (2) | C17—C16A—H'B | 111.2 |
C13—N4—H4N | 116.9 (19) | C15A—C16A—H'B | 111.2 |
C12—N4—H4N | 120 (2) | H'A—C16A—H'B | 109.1 |
C13—N5—N6 | 118.65 (19) | C16A—C15A—C20 | 109.9 (5) |
C13—N5—H5N | 115.8 (19) | C16A—C15A—C14 | 108.5 (5) |
N6—N5—H5N | 121.0 (19) | C20—C15A—C14 | 100.8 (4) |
C14—N6—N5 | 116.6 (2) | C16A—C15A—H15A | 112.3 |
N4—C12—H12A | 109.5 | C20—C15A—H15A | 112.3 |
N4—C12—H12B | 109.5 | C14—C15A—H15A | 112.3 |
C2—N2—N3—C3 | 170.57 (19) | N5—N6—C14—C15A | 178.7 (3) |
C1—N1—C2—N2 | −173.5 (2) | C19—C18—C17—C16A | 27.5 (4) |
C1—N1—C2—S1 | 4.8 (3) | C21—C18—C17—C16A | −151.8 (3) |
N3—N2—C2—N1 | −5.8 (3) | C19—C18—C17—C16 | −15.7 (4) |
N3—N2—C2—S1 | 175.83 (14) | C21—C18—C17—C16 | 164.9 (2) |
N2—N3—C3—C4 | 175.21 (17) | C17—C18—C19—C20 | −1.1 (4) |
N2—N3—C3—C11 | −3.9 (3) | C21—C18—C19—C20 | 178.3 (2) |
N3—C3—C4—C5 | 11.3 (3) | C18—C19—C20—C15 | −17.6 (4) |
C11—C3—C4—C5 | −169.5 (2) | C18—C19—C20—C15A | 10.6 (5) |
N3—C3—C4—C9 | −113.2 (2) | N6—C14—C15—C16 | 18.1 (4) |
C11—C3—C4—C9 | 66.0 (3) | C22—C14—C15—C16 | −159.0 (3) |
C3—C4—C5—C6 | 176.5 (3) | N6—C14—C15—C20 | −100.1 (4) |
C9—C4—C5—C6 | −58.4 (3) | C22—C14—C15—C20 | 82.8 (4) |
C4—C5—C6—C7 | 38.2 (4) | C19—C20—C15—C14 | 172.7 (3) |
C5—C6—C7—C8 | −11.7 (5) | C19—C20—C15—C16 | 51.9 (4) |
C5—C6—C7—C10 | 171.3 (3) | C14—C15—C16—C17 | 168.9 (3) |
C6—C7—C8—C9 | 6.3 (5) | C20—C15—C16—C17 | −68.4 (4) |
C10—C7—C8—C9 | −176.6 (3) | C18—C17—C16—C15 | 51.0 (4) |
C7—C8—C9—C4 | −27.9 (4) | C18—C17—C16A—C15A | −60.7 (5) |
C3—C4—C9—C8 | −178.6 (2) | C17—C16A—C15A—C20 | 72.4 (6) |
C5—C4—C9—C8 | 53.7 (3) | C17—C16A—C15A—C14 | −178.2 (4) |
C13—N5—N6—C14 | −174.5 (2) | C19—C20—C15A—C16A | −47.0 (6) |
C12—N4—C13—N5 | 179.7 (2) | C19—C20—C15A—C14 | −161.3 (3) |
C12—N4—C13—S2 | 2.7 (3) | N6—C14—C15A—C16A | 111.6 (5) |
N6—N5—C13—N4 | 11.6 (3) | C22—C14—C15A—C16A | −74.1 (6) |
N6—N5—C13—S2 | −171.21 (15) | N6—C14—C15A—C20 | −133.0 (4) |
N5—N6—C14—C15 | −173.2 (2) | C22—C14—C15A—C20 | 41.4 (7) |
N5—N6—C14—C22 | 3.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N3 | 0.87 (3) | 2.28 (3) | 2.645 (3) | 105 (2) |
N4—H4N···N6 | 0.87 (3) | 2.24 (3) | 2.637 (3) | 107 (2) |
N2—H2N···S2i | 0.89 (3) | 2.54 (3) | 3.4284 (19) | 172 (2) |
N4—H4N···S1ii | 0.87 (3) | 2.60 (3) | 3.337 (2) | 143 (2) |
N5—H5N···S1iii | 0.86 (3) | 2.72 (3) | 3.547 (2) | 161 (2) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+1, y−1/2, −z+1/2. |
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