5,17-Dibromo-26,28-bis-[(meth-oxy-carbon-yl)meth-oxy]-25,27-diprop-oxy-2,8,14,20-tetra-thia-calix[4]arene.

The title thia-calix[4]arene derivative, C(36)H(34)Br(2)O(8)S(4), adopts an unusual pinched cone conformation with the prop-oxy-substituted benzene rings inclined inward [forming a dihedral angle of 33.4 (1)°] and with the brominated benzene rings bent outward, making a dihedral angle of 66.1 (1)°. In the crystal, the mol-ecules form chains along [001] via C-H⋯S hydrogen bonds and S⋯S contacts [S⋯S = 3.492 (3) Å]. The chains are associated into bilayers through C-H⋯O hydrogen bonds, generating an R(2) (2)(10) motif.

Related literature

For general background to the chemistry of thia­calix[4]arenes, see: Shokova & Kovalev (2003 ▶); Lhoták (2004 ▶); Morohashi et al. (2006 ▶); Kajiwara et al. (2007 ▶); Guo et al. (2007 ▶). For related structures, see: Lhoták et al. (2000 ▶, 2003 ▶); Himl et al. (2005 ▶); Xu et al. (2008 ▶); Chen et al. (2010 ▶); Liu et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Hu et al. (2009 ▶). For atomic van der Waals radii, see: Bondi (1964 ▶).

Experimental

Crystal data

C36H34Br2O8S4

M = 882.69

Monoclinic,

a = 16.024 (3) Å

b = 14.808 (3) Å

c = 15.872 (3) Å

β = 100.065 (3)°

V = 3708.3 (12) Å3

Z = 4

Mo Kα radiation

μ = 2.46 mm−1

T = 173 K

0.38 × 0.18 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.455, T max = 0.740

19322 measured reflections

6989 independent reflections

4908 reflections with I > 2σ(I)

R int = 0.060

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.091

S = 0.93

6989 reflections

455 parameters

H-atom parameters constrained

Δρmax = 0.62 e Å−3

Δρmin = −0.55 e Å−3

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014559/ld2052sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014559/ld2052Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C36H34Br2O8S4	F(000) = 1792
Mr = 882.69	Dx = 1.581 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.024 (3) Å	Cell parameters from 4762 reflections
b = 14.808 (3) Å	θ = 2.4–24.5°
c = 15.872 (3) Å	µ = 2.46 mm−1
β = 100.065 (3)°	T = 173 K
V = 3708.3 (12) Å3	Block, colourless
Z = 4	0.38 × 0.18 × 0.13 mm

Bruker SMART CCD area-detector diffractometer	6989 independent reflections
Radiation source: fine-focus sealed tube	4908 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
phi and ω scans	θmax = 25.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −19→10
Tmin = 0.455, Tmax = 0.740	k = −18→17
19322 measured reflections	l = −17→19

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H-atom parameters constrained
S = 0.93	w = 1/[σ2(Fo2) + (0.0393P)2] where P = (Fo2 + 2Fc2)/3
6989 reflections	(Δ/σ)max = 0.001
455 parameters	Δρmax = 0.62 e Å−3
0 restraints	Δρmin = −0.55 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.11682 (2)	0.60398 (2)	0.21293 (2)	0.04232 (12)
Br2	0.03760 (2)	0.38070 (3)	1.04064 (3)	0.04869 (13)
C1	0.20213 (19)	0.6405 (2)	0.4739 (2)	0.0258 (7)
C2	0.16788 (18)	0.6550 (2)	0.38842 (19)	0.0271 (7)
H2	0.1460	0.7128	0.3702	0.033*
C3	0.16546 (19)	0.5857 (2)	0.32980 (19)	0.0274 (7)
C4	0.19244 (19)	0.5003 (2)	0.35546 (19)	0.0285 (7)
H4	0.1884	0.4527	0.3148	0.034*
C5	0.22583 (19)	0.48368 (19)	0.44142 (19)	0.0255 (7)
C6	0.23380 (18)	0.5547 (2)	0.49994 (19)	0.0256 (7)
C7	0.17985 (19)	0.3580 (2)	0.54785 (18)	0.0235 (7)
C8	0.1014 (2)	0.4000 (2)	0.5355 (2)	0.0301 (8)
H8	0.0837	0.4348	0.4852	0.036*
C9	0.0489 (2)	0.3920 (2)	0.5948 (2)	0.0324 (8)
H9	−0.0048	0.4209	0.5852	0.039*
C10	0.0742 (2)	0.3419 (2)	0.6690 (2)	0.0310 (8)
H10	0.0381	0.3367	0.7104	0.037*
C11	0.1524 (2)	0.2996 (2)	0.68202 (19)	0.0271 (7)
C12	0.20550 (19)	0.30606 (19)	0.62144 (19)	0.0242 (7)
C13	0.1789 (2)	0.3319 (2)	0.85101 (19)	0.0272 (7)
C14	0.12273 (19)	0.3240 (2)	0.90827 (19)	0.0298 (8)
H14	0.0927	0.2692	0.9118	0.036*
C15	0.1109 (2)	0.3961 (2)	0.9597 (2)	0.0295 (8)
C16	0.1492 (2)	0.4789 (2)	0.95107 (19)	0.0306 (8)
H16	0.1377	0.5292	0.9844	0.037*
C17	0.20401 (19)	0.4872 (2)	0.89340 (19)	0.0267 (7)
C18	0.22386 (19)	0.4120 (2)	0.84720 (19)	0.0246 (7)
C19	0.1805 (2)	0.62323 (19)	0.77646 (19)	0.0270 (7)
C20	0.0935 (2)	0.6079 (2)	0.7646 (2)	0.0320 (8)
H20	0.0688	0.5829	0.8096	0.038*
C21	0.0431 (2)	0.6290 (2)	0.6875 (2)	0.0347 (8)
H21	−0.0162	0.6181	0.6795	0.042*
C22	0.0782 (2)	0.6657 (2)	0.6223 (2)	0.0315 (8)
H22	0.0430	0.6797	0.5693	0.038*
C23	0.1646 (2)	0.68234 (19)	0.63296 (19)	0.0264 (7)
C24	0.21621 (19)	0.6616 (2)	0.7109 (2)	0.0249 (7)
C25	0.3470 (2)	0.5133 (2)	0.6152 (2)	0.0320 (8)
H25A	0.3524	0.4502	0.5965	0.038*
H25B	0.3578	0.5140	0.6786	0.038*
C26	0.4131 (2)	0.5699 (2)	0.5838 (2)	0.0358 (8)
C27	0.5595 (2)	0.5920 (3)	0.5987 (3)	0.0608 (12)
H27A	0.5548	0.5831	0.5369	0.091*
H27B	0.6126	0.5655	0.6283	0.091*
H27C	0.5588	0.6568	0.6113	0.091*
C28	0.2829 (2)	0.1705 (2)	0.6167 (2)	0.0519 (11)
H28A	0.2342	0.1425	0.6375	0.062*
H28B	0.2753	0.1611	0.5541	0.062*
C29	0.3602 (3)	0.1274 (3)	0.6572 (3)	0.0784 (16)
H29A	0.3724	0.1453	0.7182	0.094*
H29B	0.4075	0.1491	0.6300	0.094*
C30	0.3564 (3)	0.0260 (3)	0.6516 (3)	0.0887 (17)
H30A	0.3166	0.0032	0.6869	0.133*
H30B	0.4129	0.0009	0.6722	0.133*
H30C	0.3373	0.0079	0.5919	0.133*
C31	0.3558 (2)	0.3663 (2)	0.8103 (2)	0.0387 (9)
H31A	0.3885	0.3744	0.7634	0.046*
H31B	0.3375	0.3024	0.8097	0.046*
C32	0.4124 (2)	0.3854 (2)	0.8935 (2)	0.0351 (8)
C33	0.5475 (2)	0.3478 (3)	0.9742 (2)	0.0577 (11)
H33A	0.5603	0.4115	0.9871	0.087*
H33B	0.5993	0.3163	0.9663	0.087*
H33C	0.5250	0.3202	1.0217	0.087*
C34	0.3351 (2)	0.7543 (2)	0.7622 (2)	0.0371 (9)
H34A	0.3119	0.7636	0.8155	0.045*
H34B	0.3190	0.8067	0.7241	0.045*
C35	0.4294 (2)	0.7450 (2)	0.7823 (2)	0.0397 (9)
H35A	0.4516	0.7370	0.7284	0.048*
H35B	0.4443	0.6906	0.8179	0.048*
C36	0.4710 (2)	0.8276 (3)	0.8296 (2)	0.0508 (10)
H36A	0.4612	0.8806	0.7922	0.076*
H36B	0.5321	0.8171	0.8459	0.076*
H36C	0.4465	0.8381	0.8812	0.076*
O1	0.26345 (13)	0.54324 (13)	0.58541 (13)	0.0284 (5)
O2	0.28416 (13)	0.26639 (13)	0.63464 (13)	0.0300 (5)
O3	0.28207 (13)	0.42264 (14)	0.79386 (13)	0.0307 (5)
O4	0.30214 (13)	0.67228 (13)	0.72072 (13)	0.0302 (5)
O5	0.40072 (16)	0.62414 (17)	0.52780 (17)	0.0546 (7)
O6	0.48904 (15)	0.54881 (17)	0.62764 (17)	0.0510 (7)
O7	0.39604 (17)	0.4311 (2)	0.94997 (18)	0.0649 (8)
O8	0.48456 (15)	0.34097 (18)	0.89600 (15)	0.0484 (7)
S1	0.25109 (5)	0.37085 (5)	0.47437 (5)	0.0301 (2)
S2	0.20796 (5)	0.73180 (5)	0.54737 (5)	0.0321 (2)
S3	0.18647 (6)	0.24030 (5)	0.77987 (5)	0.0335 (2)
S4	0.24789 (5)	0.59458 (6)	0.87516 (5)	0.0325 (2)

	U11	U22	U33	U12	U13	U23
Br1	0.0565 (3)	0.0436 (2)	0.02588 (19)	0.00021 (18)	0.00459 (16)	0.00639 (16)
Br2	0.0532 (3)	0.0523 (3)	0.0492 (2)	0.01553 (19)	0.03265 (19)	0.0158 (2)
C1	0.0273 (19)	0.0213 (16)	0.0312 (18)	−0.0038 (14)	0.0115 (14)	0.0021 (15)
C2	0.0270 (19)	0.0239 (17)	0.0325 (18)	−0.0030 (14)	0.0110 (14)	0.0077 (15)
C3	0.0261 (19)	0.0338 (19)	0.0229 (17)	−0.0051 (15)	0.0063 (13)	0.0046 (15)
C4	0.039 (2)	0.0250 (17)	0.0244 (17)	−0.0048 (15)	0.0142 (14)	−0.0011 (15)
C5	0.0321 (19)	0.0210 (16)	0.0260 (17)	−0.0008 (14)	0.0121 (14)	0.0032 (14)
C6	0.0243 (18)	0.0281 (18)	0.0257 (17)	−0.0035 (14)	0.0082 (13)	0.0027 (15)
C7	0.0315 (19)	0.0198 (16)	0.0197 (16)	−0.0062 (14)	0.0055 (13)	−0.0032 (13)
C8	0.035 (2)	0.0293 (18)	0.0250 (17)	−0.0039 (16)	0.0022 (14)	0.0053 (15)
C9	0.029 (2)	0.0337 (19)	0.0345 (19)	0.0021 (15)	0.0055 (15)	−0.0005 (16)
C10	0.034 (2)	0.0300 (18)	0.0306 (19)	−0.0040 (16)	0.0103 (15)	−0.0032 (16)
C11	0.039 (2)	0.0210 (16)	0.0211 (17)	−0.0035 (15)	0.0035 (14)	0.0017 (14)
C12	0.0273 (19)	0.0165 (15)	0.0277 (18)	−0.0018 (14)	0.0016 (14)	−0.0037 (14)
C13	0.036 (2)	0.0268 (18)	0.0195 (16)	0.0079 (15)	0.0070 (14)	0.0024 (14)
C14	0.034 (2)	0.0289 (18)	0.0265 (18)	0.0023 (15)	0.0046 (14)	0.0085 (15)
C15	0.0284 (19)	0.038 (2)	0.0251 (17)	0.0109 (16)	0.0115 (14)	0.0097 (16)
C16	0.035 (2)	0.0345 (19)	0.0229 (17)	0.0092 (16)	0.0076 (14)	0.0015 (15)
C17	0.0302 (19)	0.0282 (17)	0.0212 (16)	0.0005 (15)	0.0031 (13)	0.0029 (14)
C18	0.0244 (18)	0.0294 (18)	0.0202 (16)	0.0012 (15)	0.0046 (13)	0.0049 (14)
C19	0.034 (2)	0.0234 (17)	0.0234 (17)	0.0015 (14)	0.0048 (14)	−0.0048 (14)
C20	0.032 (2)	0.035 (2)	0.0316 (19)	−0.0015 (15)	0.0131 (15)	−0.0010 (16)
C21	0.024 (2)	0.043 (2)	0.038 (2)	−0.0020 (16)	0.0079 (15)	−0.0034 (17)
C22	0.034 (2)	0.0298 (19)	0.0292 (18)	0.0025 (15)	0.0028 (15)	−0.0009 (15)
C23	0.034 (2)	0.0200 (17)	0.0274 (17)	0.0011 (14)	0.0107 (14)	−0.0061 (14)
C24	0.0236 (19)	0.0209 (17)	0.0316 (18)	−0.0014 (14)	0.0090 (14)	−0.0056 (14)
C25	0.037 (2)	0.0294 (18)	0.0289 (18)	0.0020 (16)	0.0050 (15)	−0.0006 (15)
C26	0.039 (2)	0.037 (2)	0.031 (2)	−0.0001 (17)	0.0063 (16)	−0.0057 (18)
C27	0.036 (3)	0.080 (3)	0.068 (3)	−0.004 (2)	0.014 (2)	−0.002 (3)
C28	0.057 (3)	0.047 (2)	0.047 (2)	0.013 (2)	−0.004 (2)	−0.013 (2)
C29	0.085 (4)	0.065 (3)	0.079 (4)	0.032 (3)	−0.005 (3)	−0.006 (3)
C30	0.120 (4)	0.050 (3)	0.099 (4)	0.039 (3)	0.028 (3)	0.011 (3)
C31	0.030 (2)	0.052 (2)	0.036 (2)	0.0029 (17)	0.0106 (15)	−0.0085 (18)
C32	0.031 (2)	0.037 (2)	0.038 (2)	0.0011 (16)	0.0076 (16)	−0.0040 (17)
C33	0.045 (3)	0.067 (3)	0.057 (3)	0.006 (2)	−0.005 (2)	−0.001 (2)
C34	0.034 (2)	0.0312 (19)	0.048 (2)	−0.0075 (16)	0.0108 (16)	−0.0112 (17)
C35	0.037 (2)	0.046 (2)	0.037 (2)	−0.0095 (17)	0.0083 (16)	−0.0046 (18)
C36	0.046 (3)	0.057 (3)	0.050 (2)	−0.017 (2)	0.0107 (19)	−0.012 (2)
O1	0.0318 (13)	0.0296 (12)	0.0246 (12)	0.0010 (10)	0.0075 (9)	0.0009 (10)
O2	0.0325 (14)	0.0259 (12)	0.0321 (13)	0.0025 (10)	0.0067 (10)	0.0012 (10)
O3	0.0303 (14)	0.0371 (13)	0.0271 (12)	0.0034 (10)	0.0117 (10)	0.0021 (11)
O4	0.0267 (13)	0.0298 (12)	0.0350 (13)	−0.0019 (10)	0.0077 (10)	−0.0067 (10)
O5	0.0452 (17)	0.0675 (19)	0.0517 (17)	−0.0077 (14)	0.0100 (13)	0.0237 (15)
O6	0.0332 (16)	0.0567 (17)	0.0619 (18)	0.0023 (13)	0.0050 (13)	0.0099 (14)
O7	0.0580 (19)	0.086 (2)	0.0473 (17)	0.0177 (16)	0.0002 (14)	−0.0265 (17)
O8	0.0379 (16)	0.0612 (17)	0.0436 (15)	0.0107 (13)	0.0006 (12)	−0.0088 (14)
S1	0.0435 (5)	0.0230 (4)	0.0264 (4)	0.0019 (4)	0.0135 (4)	0.0013 (4)
S2	0.0447 (6)	0.0226 (4)	0.0313 (5)	−0.0038 (4)	0.0131 (4)	−0.0007 (4)
S3	0.0530 (6)	0.0247 (4)	0.0237 (4)	0.0024 (4)	0.0095 (4)	0.0026 (4)
S4	0.0393 (5)	0.0310 (5)	0.0258 (4)	−0.0033 (4)	0.0023 (4)	−0.0023 (4)

Br1—C3	1.902 (3)	C22—H22	0.9500
Br2—C15	1.900 (3)	C23—C24	1.396 (4)
C1—C2	1.389 (4)	C23—S2	1.787 (3)
C1—C6	1.404 (4)	C24—O4	1.368 (3)
C1—S2	1.776 (3)	C25—O1	1.411 (3)
C2—C3	1.381 (4)	C25—C26	1.501 (5)
C2—H2	0.9500	C25—H25A	0.9900
C3—C4	1.375 (4)	C25—H25B	0.9900
C4—C5	1.398 (4)	C26—O5	1.189 (4)
C4—H4	0.9500	C26—O6	1.329 (4)
C5—C6	1.394 (4)	C27—O6	1.440 (4)
C5—S1	1.776 (3)	C27—H27A	0.9800
C6—O1	1.367 (3)	C27—H27B	0.9800
C7—C8	1.385 (4)	C27—H27C	0.9800
C7—C12	1.399 (4)	C28—C29	1.442 (5)
C7—S1	1.779 (3)	C28—O2	1.447 (4)
C8—C9	1.374 (4)	C28—H28A	0.9900
C8—H8	0.9500	C28—H28B	0.9900
C9—C10	1.391 (4)	C29—C30	1.505 (5)
C9—H9	0.9500	C29—H29A	0.9900
C10—C11	1.383 (4)	C29—H29B	0.9900
C10—H10	0.9500	C30—H30A	0.9800
C11—C12	1.394 (4)	C30—H30B	0.9800
C11—S3	1.785 (3)	C30—H30C	0.9800
C12—O2	1.373 (3)	C31—O3	1.432 (4)
C13—C14	1.392 (4)	C31—C32	1.494 (4)
C13—C18	1.395 (4)	C31—H31A	0.9900
C13—S3	1.782 (3)	C31—H31B	0.9900
C14—C15	1.377 (4)	C32—O7	1.188 (4)
C14—H14	0.9500	C32—O8	1.325 (4)
C15—C16	1.389 (4)	C33—O8	1.460 (4)
C16—C17	1.381 (4)	C33—H33A	0.9800
C16—H16	0.9500	C33—H33B	0.9800
C17—C18	1.400 (4)	C33—H33C	0.9800
C17—S4	1.783 (3)	C34—O4	1.437 (3)
C18—O3	1.374 (4)	C34—C35	1.496 (4)
C19—C24	1.393 (4)	C34—H34A	0.9900
C19—C20	1.393 (4)	C34—H34B	0.9900
C19—S4	1.791 (3)	C35—C36	1.526 (4)
C20—C21	1.379 (4)	C35—H35A	0.9900
C20—H20	0.9500	C35—H35B	0.9900
C21—C22	1.373 (4)	C36—H36A	0.9800
C21—H21	0.9500	C36—H36B	0.9800
C22—C23	1.388 (4)	C36—H36C	0.9800
C2—C1—C6	119.2 (3)	C26—C25—H25A	108.9
C2—C1—S2	119.4 (2)	O1—C25—H25B	108.9
C6—C1—S2	121.4 (2)	C26—C25—H25B	108.9
C3—C2—C1	120.2 (3)	H25A—C25—H25B	107.7
C3—C2—H2	119.9	O5—C26—O6	124.6 (3)
C1—C2—H2	119.9	O5—C26—C25	126.1 (3)
C4—C3—C2	120.9 (3)	O6—C26—C25	109.3 (3)
C4—C3—Br1	118.3 (2)	O6—C27—H27A	109.5
C2—C3—Br1	120.7 (2)	O6—C27—H27B	109.5
C3—C4—C5	119.9 (3)	H27A—C27—H27B	109.5
C3—C4—H4	120.1	O6—C27—H27C	109.5
C5—C4—H4	120.1	H27A—C27—H27C	109.5
C6—C5—C4	119.5 (3)	H27B—C27—H27C	109.5
C6—C5—S1	121.6 (2)	C29—C28—O2	111.4 (3)
C4—C5—S1	118.8 (2)	C29—C28—H28A	109.3
O1—C6—C5	122.9 (3)	O2—C28—H28A	109.3
O1—C6—C1	116.7 (3)	C29—C28—H28B	109.3
C5—C6—C1	120.1 (3)	O2—C28—H28B	109.3
C8—C7—C12	119.5 (3)	H28A—C28—H28B	108.0
C8—C7—S1	121.9 (2)	C28—C29—C30	113.1 (4)
C12—C7—S1	118.5 (2)	C28—C29—H29A	108.9
C9—C8—C7	120.9 (3)	C30—C29—H29A	108.9
C9—C8—H8	119.6	C28—C29—H29B	108.9
C7—C8—H8	119.6	C30—C29—H29B	108.9
C8—C9—C10	120.3 (3)	H29A—C29—H29B	107.8
C8—C9—H9	119.9	C29—C30—H30A	109.5
C10—C9—H9	119.9	C29—C30—H30B	109.5
C11—C10—C9	119.3 (3)	H30A—C30—H30B	109.5
C11—C10—H10	120.3	C29—C30—H30C	109.5
C9—C10—H10	120.3	H30A—C30—H30C	109.5
C10—C11—C12	120.8 (3)	H30B—C30—H30C	109.5
C10—C11—S3	118.9 (2)	O3—C31—C32	113.9 (3)
C12—C11—S3	120.2 (2)	O3—C31—H31A	108.8
O2—C12—C11	121.4 (3)	C32—C31—H31A	108.8
O2—C12—C7	119.4 (3)	O3—C31—H31B	108.8
C11—C12—C7	119.2 (3)	C32—C31—H31B	108.8
C14—C13—C18	119.8 (3)	H31A—C31—H31B	107.7
C14—C13—S3	118.3 (2)	O7—C32—O8	124.6 (3)
C18—C13—S3	121.8 (2)	O7—C32—C31	126.5 (3)
C15—C14—C13	119.6 (3)	O8—C32—C31	108.9 (3)
C15—C14—H14	120.2	O8—C33—H33A	109.5
C13—C14—H14	120.2	O8—C33—H33B	109.5
C14—C15—C16	121.1 (3)	H33A—C33—H33B	109.5
C14—C15—Br2	118.3 (2)	O8—C33—H33C	109.5
C16—C15—Br2	120.6 (2)	H33A—C33—H33C	109.5
C17—C16—C15	119.2 (3)	H33B—C33—H33C	109.5
C17—C16—H16	120.4	O4—C34—C35	107.3 (3)
C15—C16—H16	120.4	O4—C34—H34A	110.3
C16—C17—C18	120.4 (3)	C35—C34—H34A	110.3
C16—C17—S4	120.1 (2)	O4—C34—H34B	110.3
C18—C17—S4	119.5 (2)	C35—C34—H34B	110.3
O3—C18—C13	122.4 (3)	H34A—C34—H34B	108.5
O3—C18—C17	118.2 (3)	C34—C35—C36	111.7 (3)
C13—C18—C17	119.2 (3)	C34—C35—H35A	109.3
C24—C19—C20	119.9 (3)	C36—C35—H35A	109.3
C24—C19—S4	119.1 (2)	C34—C35—H35B	109.3
C20—C19—S4	121.0 (3)	C36—C35—H35B	109.3
C21—C20—C19	120.0 (3)	H35A—C35—H35B	107.9
C21—C20—H20	120.0	C35—C36—H36A	109.5
C19—C20—H20	120.0	C35—C36—H36B	109.5
C22—C21—C20	120.4 (3)	H36A—C36—H36B	109.5
C22—C21—H21	119.8	C35—C36—H36C	109.5
C20—C21—H21	119.8	H36A—C36—H36C	109.5
C21—C22—C23	120.6 (3)	H36B—C36—H36C	109.5
C21—C22—H22	119.7	C6—O1—C25	121.1 (2)
C23—C22—H22	119.7	C12—O2—C28	114.1 (2)
C22—C23—C24	119.5 (3)	C18—O3—C31	116.6 (2)
C22—C23—S2	119.5 (2)	C24—O4—C34	115.6 (2)
C24—C23—S2	121.0 (2)	C26—O6—C27	115.2 (3)
O4—C24—C19	119.9 (3)	C32—O8—C33	117.4 (3)
O4—C24—C23	120.2 (3)	C5—S1—C7	98.88 (14)
C19—C24—C23	119.6 (3)	C1—S2—C23	101.78 (14)
O1—C25—C26	113.4 (3)	C13—S3—C11	97.62 (14)
O1—C25—H25A	108.9	C17—S4—C19	99.14 (14)
C6—C1—C2—C3	−0.3 (4)	C20—C21—C22—C23	−0.2 (5)
S2—C1—C2—C3	177.8 (2)	C21—C22—C23—C24	0.0 (5)
C1—C2—C3—C4	3.6 (5)	C21—C22—C23—S2	−179.0 (2)
C1—C2—C3—Br1	178.8 (2)	C20—C19—C24—O4	−176.6 (3)
C2—C3—C4—C5	−2.4 (5)	S4—C19—C24—O4	3.6 (4)
Br1—C3—C4—C5	−177.8 (2)	C20—C19—C24—C23	−1.6 (4)
C3—C4—C5—C6	−1.9 (5)	S4—C19—C24—C23	178.6 (2)
C3—C4—C5—S1	174.3 (2)	C22—C23—C24—O4	175.9 (3)
C4—C5—C6—O1	178.0 (3)	S2—C23—C24—O4	−5.2 (4)
S1—C5—C6—O1	1.8 (4)	C22—C23—C24—C19	0.9 (4)
C4—C5—C6—C1	5.2 (4)	S2—C23—C24—C19	179.9 (2)
S1—C5—C6—C1	−170.9 (2)	O1—C25—C26—O5	−13.4 (5)
C2—C1—C6—O1	−177.3 (3)	O1—C25—C26—O6	167.7 (2)
S2—C1—C6—O1	4.7 (4)	O2—C28—C29—C30	171.2 (4)
C2—C1—C6—C5	−4.1 (4)	O3—C31—C32—O7	12.0 (5)
S2—C1—C6—C5	177.9 (2)	O3—C31—C32—O8	−169.7 (3)
C12—C7—C8—C9	0.7 (4)	O4—C34—C35—C36	−178.0 (3)
S1—C7—C8—C9	−177.3 (2)	C5—C6—O1—C25	63.4 (4)
C7—C8—C9—C10	0.4 (5)	C1—C6—O1—C25	−123.6 (3)
C8—C9—C10—C11	−0.5 (5)	C26—C25—O1—C6	54.1 (4)
C9—C10—C11—C12	−0.6 (5)	C11—C12—O2—C28	80.2 (4)
C9—C10—C11—S3	176.8 (2)	C7—C12—O2—C28	−103.3 (3)
C10—C11—C12—O2	178.3 (3)	C29—C28—O2—C12	−160.9 (3)
S3—C11—C12—O2	0.9 (4)	C13—C18—O3—C31	−64.3 (4)
C10—C11—C12—C7	1.7 (4)	C17—C18—O3—C31	121.5 (3)
S3—C11—C12—C7	−175.7 (2)	C32—C31—O3—C18	−66.1 (4)
C8—C7—C12—O2	−178.3 (3)	C19—C24—O4—C34	−86.5 (3)
S1—C7—C12—O2	−0.3 (4)	C23—C24—O4—C34	98.5 (3)
C8—C7—C12—C11	−1.7 (4)	C35—C34—O4—C24	169.0 (3)
S1—C7—C12—C11	176.3 (2)	O5—C26—O6—C27	−4.5 (5)
C18—C13—C14—C15	1.1 (4)	C25—C26—O6—C27	174.4 (3)
S3—C13—C14—C15	−175.3 (2)	O7—C32—O8—C33	0.9 (5)
C13—C14—C15—C16	5.0 (5)	C31—C32—O8—C33	−177.5 (3)
C13—C14—C15—Br2	−177.2 (2)	C6—C5—S1—C7	58.3 (3)
C14—C15—C16—C17	−4.0 (5)	C4—C5—S1—C7	−117.9 (3)
Br2—C15—C16—C17	178.2 (2)	C8—C7—S1—C5	33.4 (3)
C15—C16—C17—C18	−3.0 (4)	C12—C7—S1—C5	−144.6 (2)
C15—C16—C17—S4	175.4 (2)	C2—C1—S2—C23	131.6 (3)
C14—C13—C18—O3	178.0 (3)	C6—C1—S2—C23	−50.4 (3)
S3—C13—C18—O3	−5.8 (4)	C22—C23—S2—C1	−72.7 (3)
C14—C13—C18—C17	−7.9 (4)	C24—C23—S2—C1	108.3 (3)
S3—C13—C18—C17	168.4 (2)	C14—C13—S3—C11	118.2 (3)
C16—C17—C18—O3	−176.7 (3)	C18—C13—S3—C11	−58.1 (3)
S4—C17—C18—O3	4.9 (4)	C10—C11—S3—C13	−56.9 (3)
C16—C17—C18—C13	8.9 (4)	C12—C11—S3—C13	120.5 (3)
S4—C17—C18—C13	−169.5 (2)	C16—C17—S4—C19	−101.1 (3)
C24—C19—C20—C21	1.3 (5)	C18—C17—S4—C19	77.2 (3)
S4—C19—C20—C21	−178.8 (2)	C24—C19—S4—C17	−137.2 (3)
C19—C20—C21—C22	−0.4 (5)	C20—C19—S4—C17	43.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···S3i	0.95	2.91	3.755 (3)	149
C33—H33A···O7ii	0.98	2.58	3.551 (5)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯S3i	0.95	2.91	3.755 (3)	149
C33—H33A⋯O7ii	0.98	2.58	3.551 (5)	169

Symmetry codes: (i) ; (ii) .