5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis(2-cyano­benzyl­oxy)-2,8,14,20-tetra­thia­calix­[4]­arene-di­chloro­methane (1/2)

A new p-tert-butyl­thia­calix­[4]­arene derivative, C₇₂H₆₈N₄O₄S₄·2CH₂Cl₂, has been synthesized and is comprised of one tetra-p-tert-butyltetrakis(2-cyano­benzyl­oxy)­tetra­thia­calix­[4]arene and two di­chloro­methane mol­ecules. The calix­[4]­arene mol­ecule is centrosymmetric and adopts an unusual 1,2-alternate conformation via [pi]-[pi] interactions between adjacent cyano­phenyl rings on the lower rim of the parent thia­calix­[4]­arene system.

S1. Comment

Thiacalix[4]arenes (TCAs) have emerged very recently as new members of the well known calixarene family (Kumagai et al., 1997). It has been demonstrated that one of the remarkable results of the replacement of CH₂ by S is that TCAs can quantitatively extract transition metal ions, such as Co²⁺, Cu²⁺ and Zn²⁺, from an aqueous phase into chloroform (Morohashi et al., 2001) and, furthermore, oxidation of the sulfur bridges to sulfoxide or sulfone moieties leads to new types of ligands with potentially interesting complexation abilities (Lhotak et al., 2000).

For the parent calix[4]arene, four limit conformers (cone, partial cone, 1,2-alternate and 1,3-alternate) are found, to the best of our knowledge, however, for most tetrasubstituted calix[4]arene derivatives, the 1,2-alternate conformation is unknown (Cambridge Structural Database; Version of April 2001; Allen & Kennard, 1993). We report herein the structure of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-cyanobenzyloxy)-2,8,14,20- tetrathiacalix[4]arene–dichloromethane (1/2), (I), which adopts an unique 1,2-alternate conformation via π–π interactions between adjacent cyanophenyl rings on the lower rim of the parent thiacalix[4]arene system.

Single-crystal analysis reveals that the molecule is centrosymmetric. Two pairs of opposite aromatic rings, C1–C6/C1A–C6A and C11–C16/C11A–C16A, are parallel to each other. The dihedral angles between adjacent aromatic rings, i.e. C1–C6 and C11–C16, and C1A–C6A and C11A–C16A, are all 102.7 (1)°. Furthermore, adjacent cyanophenyl rings on the lower rim are nearly parallel, with a dihedral angle of 7.3 (2)° and the two carbonitrile groups are oriented in roughly the same direction. The four bridging S atoms are coplanar and the average distances between two adjacent S atoms, S1···S2, and two opposite S atoms, S2···S2A, are approximately 5.581 (1) and 8.409 (1) Å, respectively. The angles C5—S1—C11 and C1—S2—C15A are 101.54 (4) and 108.36 (4)°. The two dichloromethane solvent molecules do not enter the cavity, but are located on opposite sides of the thiacalix[4]arene molecule.

In conclusion, as the precursor of a new thiacalix[4]arene derivative, the title compound adopts an unusual 1,2-alternate conformation with two pairs of distal aromatic rings and two pairs of distal cyanophenyl rings being centrosymmetric. Hydrolysis of the cyanobenzyl groups on the lower rim to the benzoxy groups and the binding ability toward metal ions of the latter derivative are currently under investigation.

S2. Experimental

The title compound was synthesized by reaction of thiacalix[4]arene (TCA) with 2-bromomethylbenzonitrile in the presence of K₂CO₃ as catalyst. The solid product was collected by filtration and recrystallization from dichloromethane gave the title compound as flat colorless crystals.

S3. Refinement

H atoms were placed in calculated positions and refined as riding with C—H distances of 0.93, 0.96 and 0.97 for aromatic, methyl and methylene/dichloromethane H atoms, respectively.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of the title thiacalix[4]arene showing 35% probability displacement ellipsoids. H atoms and dichloromethane solvent molecules have been omitted for clarity.

5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis(2-cyanobenzyloxy)-2,8,14,20- tetrathiacalix[4]arene–dichloromethane (1/2)

Crystal data

C72H68N4O4S4·2CH2Cl2	F(000) = 1416
Mr = 1351.40	Dx = 1.278 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 80 reflections
a = 13.768 (4) Å	θ = 2.4–24.5°
b = 17.021 (5) Å	µ = 0.34 mm^−1
c = 15.543 (4) Å	T = 293 K
β = 105.424 (5)°	Plate, colorless
V = 3511.3 (17) Å^3	0.40 × 0.30 × 0.20 mm
Z = 2

Data collection

Bruker CCD area-detector diffractometer	6105 independent reflections
Radiation source: fine-focus sealed tube	3885 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.877, Tmax = 0.935	k = −20→15
14071 measured reflections	l = −18→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.186	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1P)^2 + 0.9P] where P = (Fo^2 + 2Fc^2)/3
6105 reflections	(Δ/σ)max = 0.052
406 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
S1	0.10101 (6)	0.17507 (5)	0.91405 (6)	0.0419 (3)
S2	−0.28260 (6)	0.11024 (5)	0.95247 (6)	0.0452 (3)
O1	−0.08264 (16)	0.07209 (12)	0.89977 (14)	0.0392 (5)
O2	0.15811 (17)	−0.00487 (13)	0.90518 (14)	0.0434 (6)
N1	−0.2570 (4)	0.1175 (3)	0.5825 (3)	0.0871 (13)
N2	0.0477 (4)	0.0988 (4)	0.6007 (3)	0.1180 (18)
C1	−0.1636 (2)	0.15912 (17)	0.9824 (2)	0.0377 (7)
C2	−0.1590 (3)	0.22621 (19)	1.0359 (2)	0.0420 (8)
C3	−0.0761 (2)	0.27638 (19)	1.0549 (2)	0.0414 (8)
C4	0.0034 (2)	0.25717 (19)	1.0190 (2)	0.0403 (8)
C5	0.0016 (2)	0.19038 (18)	0.9673 (2)	0.0361 (7)
C6	−0.0828 (2)	0.14025 (17)	0.9486 (2)	0.0351 (7)
C7	−0.0716 (3)	0.3515 (2)	1.1109 (3)	0.0525 (10)
C8	−0.0696 (5)	0.4232 (3)	1.0510 (3)	0.0896 (16)
C9	−0.1628 (4)	0.3577 (3)	1.1508 (4)	0.0984 (19)
C10	0.0237 (3)	0.3522 (3)	1.1884 (3)	0.0727 (13)
C11	0.1872 (2)	0.11592 (19)	0.9952 (2)	0.0363 (7)
C12	0.2436 (2)	0.15250 (19)	1.0734 (2)	0.0398 (8)
C13	0.3087 (2)	0.11139 (19)	1.1426 (2)	0.0411 (8)
C14	0.3127 (2)	0.03056 (19)	1.1320 (2)	0.0403 (8)
C15	0.2608 (2)	−0.00792 (19)	1.0543 (2)	0.0383 (8)
C16	0.2008 (2)	0.03557 (18)	0.9818 (2)	0.0336 (7)
C17	0.3723 (3)	0.1555 (2)	1.2254 (2)	0.0507 (9)
C18	0.3042 (4)	0.2014 (3)	1.2691 (3)	0.0765 (13)
C19	0.4389 (4)	0.0984 (3)	1.2934 (3)	0.098 (2)
C20	0.4427 (3)	0.2129 (3)	1.1949 (3)	0.0795 (14)
C21	0.1633 (3)	0.0293 (2)	0.8216 (2)	0.0533 (9)
C22	0.1859 (3)	−0.0339 (2)	0.7620 (3)	0.0541 (10)
C23	0.2409 (3)	−0.1004 (3)	0.7930 (3)	0.0704 (12)
C24	0.2619 (4)	−0.1552 (3)	0.7334 (4)	0.0904 (16)
C25	0.2281 (5)	−0.1433 (4)	0.6426 (4)	0.1033 (19)
C26	0.1714 (5)	−0.0786 (4)	0.6093 (4)	0.0944 (18)
C27	0.1507 (3)	−0.0230 (3)	0.6675 (3)	0.0664 (12)
C28	0.0925 (4)	0.0448 (4)	0.6301 (3)	0.0779 (14)
C29	−0.1298 (3)	0.08019 (19)	0.8058 (2)	0.0412 (8)
C30	−0.1148 (2)	0.0054 (2)	0.7598 (2)	0.0404 (8)
C31	−0.0617 (3)	−0.0581 (2)	0.8043 (3)	0.0500 (9)
C32	−0.0436 (3)	−0.1233 (2)	0.7573 (3)	0.0645 (11)
C33	−0.0786 (4)	−0.1265 (3)	0.6650 (3)	0.0747 (13)
C34	−0.1341 (3)	−0.0660 (3)	0.6198 (3)	0.0664 (12)
C35	−0.1531 (3)	0.0007 (2)	0.6662 (2)	0.0474 (9)
C36	−0.2107 (3)	0.0658 (3)	0.6185 (3)	0.0585 (10)
Cl1	0.4272 (4)	0.2014 (2)	0.9251 (3)	0.2541 (19)
Cl2	0.43900 (17)	0.03918 (17)	0.88973 (15)	0.1532 (8)
C37	0.4564 (5)	0.1130 (5)	0.9651 (7)	0.147 (3)
H2A	−0.2129	0.2375	1.0593	0.050*
H4A	0.0593	0.2900	1.0300	0.048*
H8A	−0.1292	0.4234	1.0021	0.134*
H8B	−0.0112	0.4204	1.0285	0.134*
H8C	−0.0670	0.4705	1.0853	0.134*
H9A	−0.1637	0.3132	1.1884	0.148*
H9B	−0.2239	0.3589	1.1034	0.148*
H9C	−0.1574	0.4050	1.1854	0.148*
H10A	0.0231	0.3079	1.2265	0.109*
H10B	0.0261	0.3998	1.2219	0.109*
H10C	0.0818	0.3492	1.1655	0.109*
H12A	0.2372	0.2065	1.0792	0.048*
H14A	0.3518	0.0009	1.1788	0.048*
H18A	0.2604	0.1658	1.2887	0.115*
H18B	0.2645	0.2378	1.2268	0.115*
H18C	0.3444	0.2298	1.3194	0.115*
H19A	0.3968	0.0618	1.3138	0.148*
H19B	0.4786	0.1276	1.3432	0.148*
H19C	0.4826	0.0702	1.2653	0.148*
H20A	0.4032	0.2495	1.1529	0.119*
H20B	0.4861	0.1840	1.1671	0.119*
H20C	0.4827	0.2409	1.2456	0.119*
H21A	0.2157	0.0690	0.8323	0.064*
H21B	0.0997	0.0543	0.7927	0.064*
H23A	0.2643	−0.1091	0.8541	0.085*
H24A	0.2990	−0.2000	0.7551	0.108*
H25A	0.2439	−0.1796	0.6036	0.124*
H26A	0.1469	−0.0719	0.5479	0.113*
H29A	−0.1000	0.1239	0.7818	0.049*
H29B	−0.2011	0.0906	0.7960	0.049*
H31A	−0.0380	−0.0571	0.8662	0.060*
H32A	−0.0075	−0.1655	0.7880	0.077*
H33A	−0.0641	−0.1698	0.6341	0.090*
H34A	−0.1595	−0.0687	0.5581	0.080*
H37A	0.4167	0.1016	1.0067	0.176*
H37B	0.5266	0.1131	0.9988	0.176*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0417 (5)	0.0436 (5)	0.0388 (5)	0.0044 (4)	0.0077 (4)	0.0045 (4)
S2	0.0348 (5)	0.0340 (4)	0.0608 (6)	0.0011 (4)	0.0025 (4)	−0.0065 (4)
O1	0.0474 (13)	0.0297 (11)	0.0344 (12)	0.0031 (10)	0.0003 (10)	−0.0043 (9)
O2	0.0446 (13)	0.0471 (13)	0.0355 (13)	−0.0055 (11)	0.0051 (10)	−0.0089 (10)
N1	0.108 (3)	0.092 (3)	0.053 (2)	0.023 (3)	0.008 (2)	0.004 (2)
N2	0.126 (4)	0.142 (5)	0.082 (3)	0.026 (4)	0.020 (3)	0.028 (3)
C1	0.0378 (18)	0.0289 (16)	0.0399 (18)	0.0003 (13)	−0.0010 (14)	−0.0016 (13)
C2	0.0436 (19)	0.0368 (18)	0.0422 (19)	0.0012 (15)	0.0056 (15)	−0.0068 (15)
C3	0.0436 (19)	0.0342 (17)	0.0411 (19)	0.0025 (15)	0.0018 (15)	−0.0065 (14)
C4	0.0405 (18)	0.0331 (17)	0.0401 (19)	−0.0045 (14)	−0.0021 (15)	−0.0012 (14)
C5	0.0360 (17)	0.0355 (17)	0.0322 (17)	0.0064 (13)	0.0008 (13)	0.0036 (13)
C6	0.0398 (18)	0.0281 (15)	0.0320 (17)	0.0031 (14)	0.0000 (13)	−0.0020 (13)
C7	0.060 (2)	0.0363 (19)	0.055 (2)	−0.0032 (17)	0.0056 (18)	−0.0156 (16)
C8	0.135 (5)	0.043 (2)	0.085 (4)	0.005 (3)	0.019 (3)	−0.011 (2)
C9	0.092 (4)	0.084 (3)	0.128 (5)	−0.012 (3)	0.044 (3)	−0.067 (3)
C10	0.083 (3)	0.061 (3)	0.064 (3)	−0.004 (2)	0.001 (2)	−0.024 (2)
C11	0.0337 (16)	0.0393 (17)	0.0363 (18)	−0.0007 (13)	0.0098 (13)	0.0006 (14)
C12	0.0395 (18)	0.0356 (17)	0.0408 (19)	−0.0047 (14)	0.0044 (15)	−0.0058 (14)
C13	0.0399 (18)	0.0380 (18)	0.0422 (19)	−0.0015 (15)	0.0050 (15)	−0.0045 (15)
C14	0.0356 (17)	0.0410 (18)	0.0397 (19)	−0.0021 (14)	0.0016 (14)	−0.0029 (15)
C15	0.0299 (16)	0.0363 (17)	0.046 (2)	−0.0028 (13)	0.0060 (14)	−0.0057 (14)
C16	0.0291 (16)	0.0367 (17)	0.0340 (17)	−0.0047 (13)	0.0069 (13)	−0.0033 (14)
C17	0.057 (2)	0.0428 (19)	0.042 (2)	−0.0073 (16)	−0.0045 (17)	−0.0085 (16)
C18	0.079 (3)	0.081 (3)	0.067 (3)	−0.016 (3)	0.015 (2)	−0.029 (2)
C19	0.117 (4)	0.069 (3)	0.069 (3)	0.002 (3)	−0.045 (3)	−0.013 (2)
C20	0.067 (3)	0.085 (3)	0.079 (3)	−0.031 (3)	0.006 (2)	−0.024 (3)
C21	0.060 (2)	0.061 (2)	0.038 (2)	−0.0021 (19)	0.0117 (17)	−0.0040 (17)
C22	0.052 (2)	0.062 (2)	0.051 (2)	−0.0120 (19)	0.0191 (18)	−0.0134 (19)
C23	0.076 (3)	0.072 (3)	0.066 (3)	0.005 (2)	0.022 (2)	−0.012 (2)
C24	0.102 (4)	0.075 (3)	0.104 (5)	0.014 (3)	0.045 (3)	−0.019 (3)
C25	0.135 (5)	0.100 (5)	0.093 (5)	−0.009 (4)	0.062 (4)	−0.042 (4)
C26	0.121 (5)	0.118 (5)	0.057 (3)	−0.016 (4)	0.046 (3)	−0.032 (3)
C27	0.071 (3)	0.083 (3)	0.052 (3)	−0.013 (2)	0.029 (2)	−0.015 (2)
C28	0.085 (3)	0.105 (4)	0.045 (3)	0.002 (3)	0.019 (2)	0.003 (3)
C29	0.0472 (19)	0.0373 (18)	0.0347 (18)	0.0028 (15)	0.0031 (15)	−0.0052 (14)
C30	0.0381 (18)	0.0410 (18)	0.042 (2)	−0.0053 (15)	0.0097 (14)	−0.0066 (15)
C31	0.053 (2)	0.0379 (19)	0.055 (2)	0.0032 (16)	0.0072 (17)	−0.0056 (16)
C32	0.066 (3)	0.046 (2)	0.080 (3)	0.0049 (19)	0.017 (2)	−0.013 (2)
C33	0.086 (3)	0.056 (3)	0.087 (4)	0.003 (2)	0.031 (3)	−0.031 (2)
C34	0.078 (3)	0.072 (3)	0.053 (2)	−0.006 (2)	0.025 (2)	−0.024 (2)
C35	0.049 (2)	0.056 (2)	0.038 (2)	−0.0046 (17)	0.0136 (16)	−0.0108 (17)
C36	0.067 (3)	0.067 (3)	0.038 (2)	0.003 (2)	0.0072 (19)	−0.009 (2)
Cl1	0.368 (5)	0.157 (2)	0.304 (4)	0.026 (3)	0.206 (4)	0.054 (3)
Cl2	0.1340 (16)	0.199 (2)	0.1280 (16)	0.0160 (15)	0.0375 (12)	0.0098 (15)
C37	0.090 (5)	0.161 (8)	0.211 (9)	−0.016 (5)	0.078 (5)	−0.012 (7)

Geometric parameters (Å, º)

S1—C11	1.794 (3)	C17—C19	1.545 (6)
S1—C5	1.797 (3)	C18—H18A	0.9600
S2—C15^i	1.775 (3)	C18—H18B	0.9600
S2—C1	1.785 (3)	C18—H18C	0.9600
O1—C6	1.386 (4)	C19—H19A	0.9600
O1—C29	1.438 (4)	C19—H19B	0.9600
O2—C16	1.365 (4)	C19—H19C	0.9600
O2—C21	1.443 (4)	C20—H20A	0.9600
N1—C36	1.141 (5)	C20—H20B	0.9600
N2—C28	1.134 (7)	C20—H20C	0.9600
C1—C6	1.388 (5)	C21—C22	1.504 (5)
C1—C2	1.404 (4)	C21—H21A	0.9700
C2—C3	1.393 (5)	C21—H21B	0.9700
C2—H2A	0.9300	C22—C23	1.377 (6)
C3—C4	1.393 (5)	C22—C27	1.432 (6)
C3—C7	1.538 (5)	C23—C24	1.398 (7)
C4—C5	1.389 (4)	C23—H23A	0.9300
C4—H4A	0.9300	C24—C25	1.378 (8)
C5—C6	1.408 (4)	C24—H24A	0.9300
C7—C10	1.527 (5)	C25—C26	1.370 (9)
C7—C9	1.545 (6)	C25—H25A	0.9300
C7—C8	1.540 (6)	C26—C27	1.390 (7)
C8—H8A	0.9600	C26—H26A	0.9300
C8—H8B	0.9600	C27—C28	1.436 (8)
C8—H8C	0.9600	C29—C30	1.501 (5)
C9—H9A	0.9600	C29—H29A	0.9700
C9—H9B	0.9600	C29—H29B	0.9700
C9—H9C	0.9600	C30—C31	1.383 (5)
C10—H10A	0.9600	C30—C35	1.412 (5)
C10—H10B	0.9600	C31—C32	1.389 (5)
C10—H10C	0.9600	C31—H31A	0.9300
C11—C12	1.401 (4)	C32—C33	1.387 (6)
C11—C16	1.404 (4)	C32—H32A	0.9300
C12—C13	1.392 (5)	C33—C34	1.362 (7)
C12—H12A	0.9300	C33—H33A	0.9300
C13—C14	1.389 (5)	C34—C35	1.406 (5)
C13—C17	1.545 (5)	C34—H34A	0.9300
C14—C15	1.393 (4)	C35—C36	1.447 (6)
C14—H14A	0.9300	Cl1—C37	1.637 (9)
C15—C16	1.417 (4)	Cl2—C37	1.691 (9)
C15—S2^i	1.775 (3)	C37—H37A	0.9700
C17—C18	1.514 (6)	C37—H37B	0.9700
C17—C20	1.536 (6)
C11—S1—C5	101.54 (14)	H18A—C18—H18B	109.5
C15^i—S2—C1	108.36 (14)	C17—C18—H18C	109.5
C6—O1—C29	114.2 (2)	H18A—C18—H18C	109.5
C16—O2—C21	118.0 (3)	H18B—C18—H18C	109.5
C6—C1—C2	119.8 (3)	C17—C19—H19A	109.5
C6—C1—S2	124.5 (2)	C17—C19—H19B	109.5
C2—C1—S2	115.3 (3)	H19A—C19—H19B	109.5
C3—C2—C1	122.0 (3)	C17—C19—H19C	109.5
C3—C2—H2A	119.0	H19A—C19—H19C	109.5
C1—C2—H2A	119.0	H19B—C19—H19C	109.5
C4—C3—C2	117.2 (3)	C17—C20—H20A	109.5
C4—C3—C7	120.3 (3)	C17—C20—H20B	109.5
C2—C3—C7	122.5 (3)	H20A—C20—H20B	109.5
C3—C4—C5	121.9 (3)	C17—C20—H20C	109.5
C3—C4—H4A	119.0	H20A—C20—H20C	109.5
C5—C4—H4A	119.0	H20B—C20—H20C	109.5
C4—C5—C6	120.2 (3)	O2—C21—C22	109.5 (3)
C4—C5—S1	119.1 (3)	O2—C21—H21A	109.8
C6—C5—S1	120.3 (2)	C22—C21—H21A	109.8
O1—C6—C1	121.2 (3)	O2—C21—H21B	109.8
O1—C6—C5	119.9 (3)	C22—C21—H21B	109.8
C1—C6—C5	118.8 (3)	H21A—C21—H21B	108.2
C10—C7—C9	107.6 (4)	C23—C22—C27	118.1 (4)
C10—C7—C3	110.5 (3)	C23—C22—C21	123.9 (4)
C9—C7—C3	111.7 (3)	C27—C22—C21	118.0 (4)
C10—C7—C8	108.7 (4)	C22—C23—C24	120.5 (5)
C9—C7—C8	109.6 (4)	C22—C23—H23A	119.7
C3—C7—C8	108.7 (3)	C24—C23—H23A	119.7
C7—C8—H8A	109.5	C25—C24—C23	120.5 (5)
C7—C8—H8B	109.5	C25—C24—H24A	119.7
H8A—C8—H8B	109.5	C23—C24—H24A	119.7
C7—C8—H8C	109.5	C24—C25—C26	120.6 (5)
H8A—C8—H8C	109.5	C24—C25—H25A	119.7
H8B—C8—H8C	109.5	C26—C25—H25A	119.7
C7—C9—H9A	109.5	C25—C26—C27	119.7 (5)
C7—C9—H9B	109.5	C25—C26—H26A	120.1
H9A—C9—H9B	109.5	C27—C26—H26A	120.1
C7—C9—H9C	109.5	C26—C27—C22	120.5 (5)
H9A—C9—H9C	109.5	C26—C27—C28	118.2 (5)
H9B—C9—H9C	109.5	C22—C27—C28	121.3 (4)
C7—C10—H10A	109.5	N2—C28—C27	179.1 (6)
C7—C10—H10B	109.5	O1—C29—C30	108.7 (3)
H10A—C10—H10B	109.5	O1—C29—H29A	109.9
C7—C10—H10C	109.5	C30—C29—H29A	109.9
H10A—C10—H10C	109.5	O1—C29—H29B	109.9
H10B—C10—H10C	109.5	C30—C29—H29B	109.9
C12—C11—C16	119.8 (3)	H29A—C29—H29B	108.3
C12—C11—S1	118.1 (2)	C31—C30—C35	118.4 (3)
C16—C11—S1	122.1 (2)	C31—C30—C29	123.0 (3)
C13—C12—C11	122.8 (3)	C35—C30—C29	118.6 (3)
C13—C12—H12A	118.6	C30—C31—C32	120.4 (4)
C11—C12—H12A	118.6	C30—C31—H31A	119.8
C14—C13—C12	116.4 (3)	C32—C31—H31A	119.8
C14—C13—C17	123.3 (3)	C33—C32—C31	120.9 (4)
C12—C13—C17	120.4 (3)	C33—C32—H32A	119.5
C13—C14—C15	122.8 (3)	C31—C32—H32A	119.5
C13—C14—H14A	118.6	C34—C33—C32	119.8 (4)
C15—C14—H14A	118.6	C34—C33—H33A	120.1
C14—C15—C16	120.1 (3)	C32—C33—H33A	120.1
C14—C15—S2^i	117.2 (2)	C33—C34—C35	120.2 (4)
C16—C15—S2^i	122.5 (2)	C33—C34—H34A	119.9
O2—C16—C11	125.3 (3)	C35—C34—H34A	119.9
O2—C16—C15	117.1 (3)	C34—C35—C30	120.3 (4)
C11—C16—C15	117.6 (3)	C34—C35—C36	120.5 (3)
C18—C17—C20	109.1 (4)	C30—C35—C36	119.3 (3)
C18—C17—C19	110.1 (4)	N1—C36—C35	178.4 (5)
C20—C17—C19	107.6 (4)	Cl1—C37—Cl2	116.4 (6)
C18—C17—C13	110.0 (3)	Cl1—C37—H37A	108.2
C20—C17—C13	108.4 (3)	Cl2—C37—H37A	108.2
C19—C17—C13	111.4 (3)	Cl1—C37—H37B	108.2
C17—C18—H18A	109.5	Cl2—C37—H37B	108.2
C17—C18—H18B	109.5	H37A—C37—H37B	107.3
C15^i—S2—C1—C6	40.8 (3)	S1—C11—C16—O2	5.6 (4)
C15^i—S2—C1—C2	−146.6 (2)	C12—C11—C16—C15	9.0 (4)
C6—C1—C2—C3	1.6 (5)	S1—C11—C16—C15	−172.2 (2)
S2—C1—C2—C3	−171.4 (3)	C14—C15—C16—O2	175.2 (3)
C1—C2—C3—C4	−0.4 (5)	S2^i—C15—C16—O2	0.9 (4)
C1—C2—C3—C7	178.0 (3)	C14—C15—C16—C11	−6.9 (4)
C2—C3—C4—C5	−0.9 (5)	S2^i—C15—C16—C11	178.9 (2)
C7—C3—C4—C5	−179.3 (3)	C14—C13—C17—C18	−122.9 (4)
C3—C4—C5—C6	1.0 (5)	C12—C13—C17—C18	57.6 (5)
C3—C4—C5—S1	173.7 (2)	C14—C13—C17—C20	117.9 (4)
C11—S1—C5—C4	93.2 (3)	C12—C13—C17—C20	−61.6 (5)
C11—S1—C5—C6	−94.1 (3)	C14—C13—C17—C19	−0.4 (5)
C29—O1—C6—C1	87.0 (4)	C12—C13—C17—C19	−179.9 (4)
C29—O1—C6—C5	−95.3 (3)	C16—O2—C21—C22	139.1 (3)
C2—C1—C6—O1	176.3 (3)	O2—C21—C22—C23	−29.9 (5)
S2—C1—C6—O1	−11.4 (4)	O2—C21—C22—C27	152.1 (3)
C2—C1—C6—C5	−1.5 (4)	C27—C22—C23—C24	0.4 (6)
S2—C1—C6—C5	170.8 (2)	C21—C22—C23—C24	−177.6 (4)
C4—C5—C6—O1	−177.5 (3)	C22—C23—C24—C25	0.2 (8)
S1—C5—C6—O1	9.8 (4)	C23—C24—C25—C26	−1.5 (9)
C4—C5—C6—C1	0.2 (4)	C24—C25—C26—C27	2.2 (9)
S1—C5—C6—C1	−172.4 (2)	C25—C26—C27—C22	−1.6 (8)
C4—C3—C7—C10	−55.3 (5)	C25—C26—C27—C28	178.9 (5)
C2—C3—C7—C10	126.4 (4)	C23—C22—C27—C26	0.3 (6)
C4—C3—C7—C9	−175.1 (4)	C21—C22—C27—C26	178.5 (4)
C2—C3—C7—C9	6.6 (5)	C23—C22—C27—C28	179.8 (4)
C4—C3—C7—C8	63.8 (5)	C21—C22—C27—C28	−2.1 (6)
C2—C3—C7—C8	−114.5 (4)	C6—O1—C29—C30	174.0 (3)
C5—S1—C11—C12	−73.6 (3)	O1—C29—C30—C31	−1.2 (5)
C5—S1—C11—C16	107.6 (3)	O1—C29—C30—C35	−178.5 (3)
C16—C11—C12—C13	−4.6 (5)	C35—C30—C31—C32	2.4 (5)
S1—C11—C12—C13	176.6 (3)	C29—C30—C31—C32	−174.9 (4)
C11—C12—C13—C14	−2.2 (5)	C30—C31—C32—C33	−0.3 (6)
C11—C12—C13—C17	177.3 (3)	C31—C32—C33—C34	−2.0 (7)
C12—C13—C14—C15	4.5 (5)	C32—C33—C34—C35	2.1 (7)
C17—C13—C14—C15	−175.0 (3)	C33—C34—C35—C30	0.0 (6)
C13—C14—C15—C16	0.0 (5)	C33—C34—C35—C36	179.1 (4)
C13—C14—C15—S2^i	174.6 (3)	C31—C30—C35—C34	−2.3 (5)
C21—O2—C16—C11	47.2 (4)	C29—C30—C35—C34	175.2 (3)
C21—O2—C16—C15	−135.0 (3)	C31—C30—C35—C36	178.7 (4)
C12—C11—C16—O2	−173.2 (3)	C29—C30—C35—C36	−3.9 (5)

Symmetry code: (i) −x, −y, −z+2.