Absolute configuration and conformational disorder of a tricyclic thio­semicarbazone derivative

The title compound, (1S,3R,8R)-2,2-dichloro-3,7,7,10-tetra­methyl­tricyclo­[6.4.0.0^1,3]­dodecan-11-one thio­semicarbazone, C₁₇H₂₅Cl₂N₃S, has two disordered conformations of the cyclo­heptane moiety and a screw-boat conformation for the cyclo­hexene ring. The absolute configuration was established.

S1. Comment

Thiosemicarbazone compounds exhibit well known pharmacological activities, such as selective inhibition of the herpes virus (Blumenkopf et al., 1992) or inhibition of human immunodeficiency virus (HIV) (Teitz et al., 1994). Within the framework of the evaluation of Moroccan natural resources, we have undertaken the synthesis and characterization of such compounds. The dichlorocyclopropanation (Auhmani et al., 2002; Eljamili et al., 2002) of β-himachalene (Plattier & Teisseire, 1974), a major sesquiterpene isolated from the essential oil of Atlantical Cedrus, followed by oxidation using N-bromosuccinimide and condensation with thiosemicarbazide, led to the title compound, (I). The structure of (I) was elucidated by ¹H and ¹³C NMR spectroscopies and its absolute configuration established by single-crystal X-ray diffraction analysis.

The overall shape of the molecule of (I) can be described as two domains, with a globular hydrophobic core consisting of three substituted fused rings and an elongated hydrophilic thiosemicarbazone tail (Fig. 1). The absolute configuration of (I) was established without ambiguity from the anomalous dispersion of the S and Cl atoms and confirmed that the stereochemistry of the ring junction atoms as C1(S), C3(R) and C8(R) (Fig. 1). The cyclohexene ring is distorted and the puckering parameters (Cremer & Pople, 1975) show that its conformation is close to that of a screw-boat: the θ and ϕ angles calculated for the atom sequence C8/C9/C10/C11/C12/C1 are 67.7 (2) and 324.4 (3)°, respectively. The thiosemicarbazone substituent on the cyclohexene ring adopts a planar zigzag conformation, with the N—H bond cis to the C═N double bond and trans to the terminal NH₂ group. This latter group makes a single hydrogen bond with the S acceptor atom of a symmetry-related molecule [symmetry code: −1/2 + x, 1/2 − y, 1 − z; Table 1]. The two remaining potential N—H donors are not involved in any inter- or intra-molecular interactions and thus the hydrogen-bonding network within the crystal of (I) can be described as an extended chain along [100] (Fig. 2).

Interestingly, the solid-state structure of (I) reveals the presence of conformational disorder for the cycloheptane ring. Both the chair and boat conformations have been trapped randomly during the crystallization process and the chair conformation occurs in 63.6 (6)% of the molecules. The chair conformation of seven-membered rings is known to be more stable than the boat conformation by a few kcal mol⁻¹ (Eliel et al., 1994; 1 kcal mol⁻¹ = 4.184 kJ mol⁻¹). Thus, the relative proportion of both conformers observed within the crystal of (I) may reflect the statistical partitioning of the two populations of cycloheptane structures corresponding to different energetic states.

Another point of interest is the comparison of the molecular structure of (I) with that of its parent compound, (II) (i.e. without the thiosemicarbazone substituent), which was reported by Auhmani et al. (1999). In this latter structure, no conformational disorder was observed and the cycloheptane ring adopts a boat conformation. The superposition of the boat conformation of (I) with compound (II) shows that they fit remarkably well: the r.m.s. deviation calculated with all pairs of corresponding C and Cl atoms of the three- and seven-membered rings, including the methyl substituents, is 0.070 Å. The main difference between the conformations of the two molecules is observed for the cyclohexene ring. The θ and ϕ puckering parameters for the cyclohexene ring of (II) [with the same reference atoms as used for (I)] are 53.5 (4) and 277.1 (4)°, respectively, and describe a distorted conformation between that of an envelope and a half-chair. The different hybridization character of the C atom, which bears the thiosemicarbazone moiety in (I) (sp² hybridization) and two H atoms in (II) (sp³ hybridization) is responsible for this difference in ring conformation. On the basis of the superposition described above, we calculated the distance between C11 in (I) and its equivalent in (II) and found it to be 0.638 Å, while the five remaining atoms of the cyclohexene ring fit well (the mean distance between corresponding C atoms is 0.108 Å).

S2. Experimental

The dichlorocyclopropanation of β-himachalene, a major sesquiterpene isolated from the essential oil of Atlantical Cedrus, was carried out using 1 equivalent of chloroform and excess sodium hydroxide in phase-transfer catalysis liquid–solid at 273 K for 2 h. The product obtained was dissolved in tetrahydrofuran (50 ml) and oxidized with 2 equivalents of N-bromosuccinimide at 273 K for 1 h. The condensation of an equimolar quantity of the resultant ketone with thiosemicarbazide and several drops of hydrochloric acid in ethanol gave (I) in 60% yield after heating at reflux for 5 h. Suitable crystals were obtained by evaporation of a hexane solution at 277 K. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 9.80, 8.00, 7.40 (3H, NH₂ and NH), 0.89 (3H, s), 1.01 (3H, s), 1.2–1.8 (6H, m), 4.90 (1H, d, J = 7.9 Hz), 1.82 (3H, s), 1.83 (3H, s), 2.60 (2H, AB system, J = 18.3 Hz); ¹³C NMR (CDCl₃, δ, p.p.m.): 31.06 (C-1), 77.57 (C-2), 31.64 (C-3), 29.81 (C-4), 18.09 (C-5), 21.38 (C-6), 39.12 (C-7), 45.66 (C-8), 136.10 (C-9), 133.10 (C-10), 147.52 (C-11), 34.06 (C-12), 25.63 (C-13), 18.09 (C-14), 16.59 (C-15), 14.24 (C-16), 179.24 (C═S).

S3. Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.98 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(parent atom). Additionally, the methyl groups were allowed to rotate freely about their parent C—C bond. The disordered atoms in the cycloheptane ring were refined using the SADI, DELU and SAME instructions of SHELXL97 (Sheldrick, 1997) with an effective standard deviation of 0.005 in order to restrain the geometric parameters to chemically reasonable values. The site occupancy factors of the chair and boat conformations refined to 0.636 (5) and 0.364 (5), respectively.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of (I), showing the atom-labelling scheme. Both cycloheptane ring conformations are depicted, with the minor boat conformation drawn with open bonds. Displacement ellipsoids are drawn at the 30% probability level. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 2. A view of the crystal packing of (I), showing the hydrogen-bonding network. Only the chair conformation of the cycloheptane is represented.

(1S,3R,8R)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0^1.3]dodecan- 11-one thiosemicarbazone

Crystal data

C17H25Cl2N3S	F(000) = 792
Mr = 374.38	Dx = 1.32 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 22028 reflections
a = 8.6379 (2) Å	θ = 1.3–26.0°
b = 13.3638 (3) Å	µ = 0.46 mm^−1
c = 16.3161 (3) Å	T = 293 K
V = 1883.49 (7) Å^3	Prism, colourless
Z = 4	0.6 × 0.6 × 0.4 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3499 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 26.0°, θmin = 2.0°
ϕ scans	h = −10→10
22028 measured reflections	k = −16→16
3671 independent reflections	l = −19→20

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.029P)^2 + 0.5086P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.072	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.16 e Å^−3
3671 reflections	Δρmin = −0.18 e Å^−3
237 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
18 restraints	Extinction coefficient: 0.033 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack & Bernardinelli (1999, 2000), with 1566 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.04 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.61062 (6)	0.53553 (4)	0.35727 (3)	0.04938 (15)
Cl2	0.61678 (7)	0.62823 (4)	0.19869 (4)	0.05206 (16)
S1	0.01291 (6)	0.21029 (4)	0.50781 (3)	0.05093 (17)
N1	−0.12818 (19)	0.37322 (14)	0.45567 (11)	0.0481 (4)
H1A	−0.1327	0.4269	0.4267	0.058*
H1B	−0.2054	0.3563	0.4859	0.058*
N2	0.11387 (19)	0.34842 (11)	0.40459 (9)	0.0379 (4)
H2	0.2014	0.3178	0.4033	0.045*
N3	0.08640 (18)	0.43189 (12)	0.35661 (10)	0.0378 (4)
C1	0.4408 (2)	0.45107 (13)	0.22520 (10)	0.0300 (4)
C2	0.5754 (2)	0.51657 (14)	0.25162 (12)	0.0352 (4)
C3	0.6087 (2)	0.41577 (13)	0.21366 (11)	0.0362 (4)
C4	0.6692 (3)	0.41131 (19)	0.12588 (14)	0.0545 (6)
H4A	0.6529	0.4750	0.1000	0.065*
H4B	0.7778	0.3961	0.1262	0.065*
C5	0.5839 (4)	0.3333 (2)	0.07489 (16)	0.0710 (8)
H5A	0.5605	0.2764	0.1097	0.085*	0.636 (6)
H5B	0.6527	0.3100	0.0319	0.085*	0.636 (6)
H5C	0.5928	0.3526	0.0178	0.085*	0.364 (6)
H5D	0.6382	0.2702	0.0811	0.085*	0.364 (6)
C7	0.2970 (3)	0.40121 (15)	0.08927 (12)	0.0481 (5)
C6A	0.4337 (4)	0.3692 (3)	0.0354 (2)	0.0673 (14)	0.636 (6)
H6A	0.3973	0.3161	−0.0002	0.081*	0.636 (6)
H6B	0.4595	0.4255	0.0005	0.081*	0.636 (6)
C6B	0.4135 (4)	0.3143 (3)	0.0926 (4)	0.057 (2)	0.364 (6)
H6C	0.4069	0.2852	0.1470	0.068*	0.364 (6)
H6D	0.3782	0.2637	0.0543	0.068*	0.364 (6)
C8	0.3504 (2)	0.48616 (13)	0.14951 (10)	0.0337 (4)
H8	0.4210	0.5291	0.1183	0.040*
C9	0.2214 (2)	0.55292 (14)	0.17914 (12)	0.0379 (4)
H9	0.1902	0.6048	0.1450	0.045*
C10	0.1493 (2)	0.54300 (15)	0.25042 (12)	0.0379 (4)
C11	0.1893 (2)	0.45791 (14)	0.30361 (11)	0.0330 (4)
C12	0.3412 (2)	0.40487 (13)	0.29175 (11)	0.0326 (4)
H12A	0.3177	0.3370	0.2771	0.039*
H12B	0.3957	0.4058	0.3430	0.039*
C13	0.0209 (3)	0.6120 (2)	0.27749 (17)	0.0658 (7)
H13A	0.0070	0.6637	0.2374	0.079*
H13B	0.0475	0.6415	0.3293	0.079*
H13C	−0.0733	0.5745	0.2831	0.079*
C14	0.6747 (3)	0.33357 (16)	0.26667 (14)	0.0475 (5)
H14A	0.7841	0.3437	0.2733	0.057*
H14B	0.6567	0.2700	0.2411	0.057*
H14C	0.6255	0.3348	0.3194	0.057*
C15A	0.2146 (7)	0.3138 (3)	0.1300 (3)	0.0659 (15)	0.636 (6)
H15A	0.1334	0.3387	0.1647	0.079*	0.636 (6)
H15B	0.2872	0.2765	0.1624	0.079*	0.636 (6)
H15C	0.1710	0.2711	0.0887	0.079*	0.636 (6)
C16A	0.1833 (6)	0.4489 (3)	0.0274 (3)	0.0678 (14)	0.636 (6)
H16A	0.1708	0.4052	−0.0188	0.081*	0.636 (6)
H16B	0.2237	0.5121	0.0092	0.081*	0.636 (6)
H16C	0.0848	0.4592	0.0533	0.081*	0.636 (6)
C15B	0.1433 (8)	0.3536 (7)	0.1163 (6)	0.067 (2)	0.364 (6)
H15D	0.1159	0.3011	0.0788	0.081*	0.364 (6)
H15E	0.0634	0.4036	0.1164	0.081*	0.364 (6)
H15F	0.1545	0.3264	0.1704	0.081*	0.364 (6)
C16B	0.2840 (11)	0.4424 (6)	0.0025 (3)	0.065 (2)	0.364 (6)
H16D	0.2438	0.3915	−0.0331	0.077*	0.364 (6)
H16E	0.3845	0.4627	−0.0163	0.077*	0.364 (6)
H16F	0.2155	0.4990	0.0023	0.077*	0.364 (6)
C17	−0.0033 (2)	0.31704 (14)	0.45372 (10)	0.0352 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0489 (3)	0.0556 (3)	0.0436 (3)	0.0026 (3)	−0.0091 (2)	−0.0099 (2)
Cl2	0.0539 (3)	0.0342 (2)	0.0681 (3)	−0.0107 (2)	−0.0020 (3)	0.0086 (2)
S1	0.0381 (3)	0.0578 (3)	0.0569 (3)	0.0008 (2)	0.0042 (2)	0.0279 (3)
N1	0.0329 (8)	0.0568 (10)	0.0548 (10)	0.0037 (8)	0.0086 (8)	0.0220 (8)
N2	0.0290 (7)	0.0429 (9)	0.0418 (8)	0.0017 (7)	0.0057 (7)	0.0127 (7)
N3	0.0348 (8)	0.0397 (8)	0.0391 (8)	0.0008 (6)	0.0035 (7)	0.0099 (7)
C1	0.0333 (9)	0.0279 (8)	0.0290 (8)	0.0002 (7)	0.0026 (6)	0.0011 (7)
C2	0.0346 (9)	0.0323 (9)	0.0388 (9)	0.0000 (7)	−0.0005 (7)	−0.0014 (8)
C3	0.0352 (9)	0.0338 (8)	0.0394 (10)	0.0037 (8)	0.0081 (8)	0.0000 (7)
C4	0.0552 (14)	0.0595 (13)	0.0488 (12)	0.0096 (11)	0.0204 (10)	−0.0007 (11)
C5	0.100 (2)	0.0646 (15)	0.0480 (13)	0.0199 (15)	0.0108 (14)	−0.0208 (12)
C7	0.0662 (14)	0.0447 (11)	0.0335 (10)	−0.0112 (10)	−0.0066 (10)	−0.0012 (9)
C6A	0.100 (3)	0.064 (2)	0.038 (2)	−0.001 (2)	0.0020 (19)	−0.0149 (19)
C6B	0.091 (5)	0.037 (3)	0.041 (3)	−0.009 (3)	−0.002 (3)	−0.011 (3)
C8	0.0401 (9)	0.0318 (8)	0.0292 (8)	−0.0042 (7)	0.0008 (7)	0.0046 (7)
C9	0.0362 (10)	0.0344 (9)	0.0431 (10)	0.0004 (8)	−0.0050 (8)	0.0127 (8)
C10	0.0319 (9)	0.0367 (9)	0.0452 (10)	0.0029 (8)	0.0007 (8)	0.0098 (8)
C11	0.0297 (8)	0.0345 (9)	0.0347 (9)	−0.0019 (8)	0.0006 (7)	0.0048 (8)
C12	0.0338 (9)	0.0337 (9)	0.0302 (8)	0.0016 (7)	0.0019 (7)	0.0067 (7)
C13	0.0507 (14)	0.0655 (15)	0.0811 (17)	0.0254 (12)	0.0189 (13)	0.0288 (13)
C14	0.0436 (11)	0.0405 (10)	0.0583 (13)	0.0120 (9)	0.0035 (10)	0.0043 (10)
C15A	0.107 (4)	0.043 (2)	0.049 (2)	−0.025 (2)	−0.018 (2)	0.0053 (18)
C16A	0.095 (4)	0.067 (3)	0.041 (2)	−0.021 (3)	−0.028 (2)	0.0095 (19)
C15B	0.088 (6)	0.060 (5)	0.054 (4)	−0.033 (5)	−0.004 (4)	0.003 (4)
C16B	0.075 (5)	0.079 (5)	0.039 (3)	−0.019 (4)	−0.002 (4)	−0.003 (3)
C17	0.0310 (9)	0.0433 (10)	0.0314 (8)	−0.0037 (8)	−0.0015 (7)	0.0061 (7)

Geometric parameters (Å, º)

Cl1—C2	1.769 (2)	C7—C8	1.571 (3)
Cl2—C2	1.7608 (19)	C6A—H6A	0.9700
S1—C17	1.6833 (19)	C6A—H6B	0.9700
N1—C17	1.315 (3)	C6B—H6C	0.9700
N1—H1A	0.8600	C6B—H6D	0.9700
N1—H1B	0.8600	C8—C9	1.507 (3)
N2—C17	1.357 (2)	C8—H8	0.9800
N2—N3	1.383 (2)	C9—C10	1.326 (3)
N2—H2	0.8600	C9—H9	0.9300
N3—C11	1.288 (2)	C10—C11	1.472 (2)
C1—C12	1.517 (2)	C10—C13	1.508 (3)
C1—C2	1.518 (2)	C11—C12	1.504 (2)
C1—C8	1.535 (2)	C12—H12A	0.9600
C1—C3	1.537 (3)	C12—H12B	0.9600
C2—C3	1.510 (2)	C13—H13A	0.9600
C3—C14	1.510 (3)	C13—H13B	0.9600
C3—C4	1.526 (3)	C13—H13C	0.9600
C4—C5	1.524 (4)	C14—H14A	0.9600
C4—H4A	0.9600	C14—H14B	0.9600
C4—H4B	0.9600	C14—H14C	0.9600
C5—C6B	1.522 (4)	C15A—H15A	0.9600
C5—C6A	1.526 (3)	C15A—H15B	0.9600
C5—H5A	0.9700	C15A—H15C	0.9600
C5—H5B	0.9700	C16A—H16A	0.9600
C5—H5C	0.9700	C16A—H16B	0.9600
C5—H5D	0.9700	C16A—H16C	0.9600
C7—C15A	1.521 (3)	C15B—H15D	0.9600
C7—C16B	1.523 (4)	C15B—H15E	0.9600
C7—C6A	1.533 (3)	C15B—H15F	0.9600
C7—C15B	1.537 (4)	C16B—H16D	0.9600
C7—C6B	1.537 (4)	C16B—H16E	0.9600
C7—C16A	1.546 (3)	C16B—H16F	0.9600
C17—N1—H1A	120.0	C7—C6B—H6C	107.3
C17—N1—H1B	120.0	C5—C6B—H6D	107.3
H1A—N1—H1B	120.0	C7—C6B—H6D	107.3
C17—N2—N3	117.09 (15)	H6C—C6B—H6D	106.9
C17—N2—H2	121.5	C9—C8—C1	107.40 (14)
N3—N2—H2	121.5	C9—C8—C7	114.30 (16)
C11—N3—N2	118.63 (15)	C1—C8—C7	115.61 (15)
C12—C1—C2	117.77 (15)	C9—C8—H8	106.3
C12—C1—C8	114.31 (15)	C1—C8—H8	106.3
C2—C1—C8	116.25 (15)	C7—C8—H8	106.3
C12—C1—C3	119.87 (15)	C10—C9—C8	124.71 (16)
C2—C1—C3	59.26 (11)	C10—C9—H9	117.6
C8—C1—C3	118.40 (15)	C8—C9—H9	117.6
C3—C2—C1	61.00 (12)	C9—C10—C11	118.95 (17)
C3—C2—Cl2	121.06 (13)	C9—C10—C13	122.77 (18)
C1—C2—Cl2	120.33 (13)	C11—C10—C13	118.19 (17)
C3—C2—Cl1	119.64 (13)	N3—C11—C10	116.25 (16)
C1—C2—Cl1	119.43 (13)	N3—C11—C12	124.15 (16)
Cl2—C2—Cl1	108.76 (10)	C10—C11—C12	119.56 (15)
C14—C3—C2	119.08 (16)	C11—C12—C1	113.28 (14)
C14—C3—C4	112.33 (17)	C11—C12—H12A	107.1
C2—C3—C4	119.02 (16)	C1—C12—H12A	109.0
C14—C3—C1	120.64 (17)	C11—C12—H12B	108.0
C2—C3—C1	59.73 (12)	C1—C12—H12B	109.9
C4—C3—C1	116.76 (17)	H12A—C12—H12B	109.5
C5—C4—C3	111.9 (2)	C10—C13—H13A	109.5
C5—C4—H4A	107.2	C10—C13—H13B	109.5
C3—C4—H4A	109.2	H13A—C13—H13B	109.5
C5—C4—H4B	109.3	C10—C13—H13C	109.5
C3—C4—H4B	109.8	H13A—C13—H13C	109.5
H4A—C4—H4B	109.5	H13B—C13—H13C	109.5
C6B—C5—C4	118.5 (3)	C3—C14—H14A	109.5
C4—C5—C6A	115.2 (3)	C3—C14—H14B	109.5
C4—C5—H5A	108.5	H14A—C14—H14B	109.5
C6A—C5—H5A	108.5	C3—C14—H14C	109.5
C4—C5—H5B	108.5	H14A—C14—H14C	109.5
C6A—C5—H5B	108.5	H14B—C14—H14C	109.5
H5A—C5—H5B	107.5	C7—C15A—H15A	109.5
C6B—C5—H5C	107.7	C7—C15A—H15B	109.5
C4—C5—H5C	107.7	H15A—C15A—H15B	109.5
C6B—C5—H5D	107.7	C7—C15A—H15C	109.5
C4—C5—H5D	107.7	H15A—C15A—H15C	109.5
H5C—C5—H5D	107.1	H15B—C15A—H15C	109.5
C15A—C7—C16B	130.5 (4)	C7—C16A—H16A	109.5
C15A—C7—C6A	113.4 (3)	C7—C16A—H16B	109.5
C16B—C7—C15B	110.7 (5)	H16A—C16A—H16B	109.5
C6A—C7—C15B	135.6 (4)	C7—C16A—H16C	109.5
C16B—C7—C6B	110.8 (4)	H16A—C16A—H16C	109.5
C15B—C7—C6B	104.0 (4)	H16B—C16A—H16C	109.5
C15A—C7—C16A	107.8 (3)	C7—C15B—H15D	109.5
C6A—C7—C16A	103.3 (3)	C7—C15B—H15E	109.5
C15A—C7—C8	114.8 (2)	H15D—C15B—H15E	109.5
C16B—C7—C8	110.0 (3)	C7—C15B—H15F	109.5
C6A—C7—C8	109.5 (2)	H15D—C15B—H15F	109.5
C15B—C7—C8	111.9 (4)	H15E—C15B—H15F	109.5
C6B—C7—C8	109.3 (3)	C7—C16B—H16D	109.5
C16A—C7—C8	107.3 (2)	C7—C16B—H16E	109.5
C5—C6A—C7	120.1 (2)	H16D—C16B—H16E	109.5
C5—C6A—H6A	107.3	C7—C16B—H16F	109.5
C7—C6A—H6A	107.3	H16D—C16B—H16F	109.5
C5—C6A—H6B	107.3	H16E—C16B—H16F	109.5
C7—C6A—H6B	107.3	N1—C17—N2	116.72 (17)
H6A—C6A—H6B	106.9	N1—C17—S1	122.64 (14)
C5—C6B—C7	120.1 (3)	N2—C17—S1	120.63 (15)
C5—C6B—H6C	107.3
C17—N2—N3—C11	−173.39 (17)	C8—C7—C6B—C5	−56.5 (5)
C12—C1—C2—C3	109.99 (17)	C12—C1—C8—C9	52.4 (2)
C8—C1—C2—C3	−108.89 (17)	C2—C1—C8—C9	−90.08 (18)
C12—C1—C2—Cl2	−138.96 (15)	C3—C1—C8—C9	−157.68 (15)
C8—C1—C2—Cl2	2.2 (2)	C12—C1—C8—C7	−76.6 (2)
C3—C1—C2—Cl2	111.05 (16)	C2—C1—C8—C7	140.98 (17)
C12—C1—C2—Cl1	0.3 (2)	C3—C1—C8—C7	73.4 (2)
C8—C1—C2—Cl1	141.44 (14)	C15A—C7—C8—C9	−75.7 (3)
C3—C1—C2—Cl1	−109.67 (15)	C16B—C7—C8—C9	82.5 (5)
C1—C2—C3—C14	−110.5 (2)	C6A—C7—C8—C9	155.4 (2)
Cl2—C2—C3—C14	139.59 (17)	C15B—C7—C8—C9	−40.9 (5)
Cl1—C2—C3—C14	−1.2 (3)	C6B—C7—C8—C9	−155.6 (2)
C1—C2—C3—C4	105.8 (2)	C16A—C7—C8—C9	44.0 (3)
Cl2—C2—C3—C4	−4.1 (3)	C15A—C7—C8—C1	49.7 (4)
Cl1—C2—C3—C4	−144.87 (17)	C16B—C7—C8—C1	−152.0 (4)
Cl2—C2—C3—C1	−109.88 (16)	C6A—C7—C8—C1	−79.1 (2)
Cl1—C2—C3—C1	109.32 (16)	C15B—C7—C8—C1	84.6 (5)
C12—C1—C3—C14	1.5 (3)	C6B—C7—C8—C1	−30.1 (3)
C2—C1—C3—C14	107.96 (19)	C16A—C7—C8—C1	169.4 (3)
C8—C1—C3—C14	−146.76 (18)	C1—C8—C9—C10	−31.7 (2)
C12—C1—C3—C2	−106.47 (18)	C7—C8—C9—C10	98.0 (2)
C8—C1—C3—C2	105.27 (17)	C8—C9—C10—C11	−3.8 (3)
C12—C1—C3—C4	143.97 (18)	C8—C9—C10—C13	179.9 (2)
C2—C1—C3—C4	−109.56 (19)	N2—N3—C11—C10	175.92 (16)
C8—C1—C3—C4	−4.3 (2)	N2—N3—C11—C12	−1.8 (3)
C14—C3—C4—C5	80.3 (2)	C9—C10—C11—N3	−157.69 (19)
C2—C3—C4—C5	−133.7 (2)	C13—C10—C11—N3	18.9 (3)
C1—C3—C4—C5	−65.2 (2)	C9—C10—C11—C12	20.2 (3)
C3—C4—C5—C6B	33.2 (4)	C13—C10—C11—C12	−163.3 (2)
C3—C4—C5—C6A	85.5 (3)	N3—C11—C12—C1	180.00 (18)
C4—C5—C6A—C7	−63.9 (4)	C10—C11—C12—C1	2.3 (2)
C15A—C7—C6A—C5	−73.4 (4)	C2—C1—C12—C11	102.49 (18)
C16A—C7—C6A—C5	170.3 (3)	C8—C1—C12—C11	−39.4 (2)
C8—C7—C6A—C5	56.2 (4)	C3—C1—C12—C11	171.16 (15)
C4—C5—C6B—C7	56.5 (5)	N3—N2—C17—N1	−4.9 (3)
C16B—C7—C6B—C5	64.9 (6)	N3—N2—C17—S1	174.35 (13)
C15B—C7—C6B—C5	−176.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···S1^i	0.86	2.59	3.348 (2)	147

Symmetry code: (i) x−1/2, −y+1/2, −z+1.