(E,E,E)-1,3,5-Tris[4-(acetyl­sulfan­yl)­styr­yl]­benzene toluene hemisolvate

The first crystal structure of a three-terminal sulfur end-capped oligo­phenyl­ene­vinyl­ene, C₃₆H₃₀O₃S₃·0.5C₇H₈, has been determined at 122 (1) K. The mol­ecular threefold symmetry is not utilized in the crystal structure. It is confirmed that the double bonds have been fully transformed into a trans configuration by iodine treatment.

S1. Comment

Sulfur end-capped oligophenylenevinylenes (OPVs) have recently aroused attention since our group has shown that transistors based on one single OPV (Kubatkin et al., 2003) can be made. Despite their potential applications in molecular electronics, only a limited number of sulfur end-capped OPVs have been reported. The title compound and higher analogues are currently being investigated as molecular components in three-terminal electronic devices, either by simply assembling gold clusters at the sulfur terminals (Novak & Feldheim, 2000) or attached between three gold electrodes manufactured by break junction techniques (Tour et al., 1995; Kergueris et al., 1999). Especially regarding the latter system, it is possible that these molecules upon assembly at the electrodes will provide devices possessing so far unknown nano-electromechanical properties.

Unlike their triple-bonded counterparts, phenylene ethynylenes, which can only exist in one geometry, OPVs can adopt several conformations as a result of the possibility of having either cis or trans conformation of each double bond. We recently reported the synthesis of a novel family of molecules, sulfur end-capped OPVs (Stuhr-Hansen, 2003; Stuhr-Hansen et al., 2003). All OPVs were prepared all-trans by treatment with a catalytically amount of iodine in boiling toluene. By this treatment, eventual cis-linkages are transformed into the thermodynamically more stable trans geometries. In order to determine the structure of the OPVs a crystal of a representative sulfur end-capped OPV, the title compound, (I)·5C₇H₈, was obtained in an appropriate quality for X-ray analysis by slow recrystallization from toluene. To our knowlegde, this is the first structure determination of a three-terminal sulfur end-capped OPV.

The structure of (I) shown in Fig. 1 confirms that all double bonds have been converted into the trans conformation by the iodine treatment. Furthermore, it the possible molecular threefold symmetry is not utilized in the crystal packing. As all three double bonds are found in trans conformations with the same bond distances (see Table 1), the lack of molecular symmetry is found in the conformations of the three 4-(acetylsufanyl)styryl groups. The angles between the planes of the side-chain phenyl groups and the central benzene ring are slightly different, viz. 2.25 (9), 9.45 (8) and 5.07 (8)°. Another difference is found in the conformation of the acetylsulfanyl groups, which can be illustrated by the torsion angles Cn5—Sn—Cn2—Cn1 (n = 1,2,3). The torsion angles shown in Table 1 and Fig. 1 illutrate that all three acetylsulfanyl groups are situated on the same side of the molecular plane, but are rotated differently. The side group including S1 differs from the other two by having a torsion angle less than 90° and thereby being on located on the other side of the plane perpendicular to the phenyl group. Only one bond distance in the acetylsulfanyl group differs, viz. Sn—Cn5. This difference seems to be related to the variation in the torsion angles just mentioned. The closer the torsion angle is to 90° the shorter is the Sn—Cn5 bond distance.

There does not seem to be any appreciable degree of conjugation between the phenyl groups via the double bonds, as the C_ethenyl—C_ph distances are all within 2 s.u. of 1.470 Å, compared with an the average double-bond distance of 1.333 (2) Å. These bond lengths (Table 1) are also in perfect agreement with the average styrylbenzene moities extracted from the Cambridge Structural Database (Version 5.26 of November 2004; Allen, 2002), where the complementary average bond lengths are 1.469 and 1.326 Å for the single and double bond, respectively.

The structure forms alternating layers of sections including the acetylsulfanyl groups (layers centered at c = 0 and c = 1/2) and sections consisting of only the aromatic groups (layers are centered at c = 1/4 and c = 3/4), as seen in Fig. 2. The packing arrangement as illustrated in Fig. 2 shows that the three long substituents of the central benzene ring make it difficult to form a dense crystal packing. Therefore, channels along the b axis in the aromatic layers are observed that accomodate toluene molecules in a disordered fashion. The disorder could be resolved into two sites related by symmetry (1/2 − x, 1/2 + y, 1/2 − z) with an occupation factor of 0.5. The toluene molecules are involved in intermolecular interactions with the phenyl groups of (I). The toluene molecules occupying one site are engaged in π–π interaction with (I) as well as acting as a hydrogen-bond donor in a C—H···π hydrogen bond, whereas toluene molecules in the other position act as hydrogen acceptors besides participating in π···π interactions with (I). No classical hydrogen-bond donors are available; hence only a few weak bonds that fall within the geometric criteria for C—H···O hydrogen bonds suggested by Steiner (1996) are observed. The five hydrogen bonds observed are listed in Table 2.

S2. Experimental

The title compound was synthesized as described by Stuhr-Hansen et al. (2003). Crystals suitable for an X-ray diffraction analysis were obtained by slow crystallization from hot toluene.

S3. Refinement

All H atoms were found in a difference Fourier map and then treated as riding atoms, with C—H distances of 0.95 Å for C_arom and 0.98 Å for C_Me. Isotropic displacement parameters for all H atoms were constrained to 1.2U_eq of the connected non-H atom (1.5U_eq for Me groups). Disordered toluene molecules were identified in the difference Fourier map. The toluene molecules are related by the symmetry operation (1/2 − x, 1/2 + y, 1/2 − z). Toluene was introduced with a fixed geometry obtained from the literature (Irngartinger et al., 1999) and initially refined as a rigid body with a fixed occupancy of 0.5. In the final model the geometrical constraints were removed and displacement parameters of all non-H atoms were refined. The occupancy factor of toluene did not change upon release and joint refinement.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and Mercury (Bruno et al., 2002); software used to prepare material for publication: program (reference)?.

Figures

	Fig. 1. ORTEP drawing (Johnson, 1976) of (I), including labelling of the atoms. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres with arbitrary radii. The disordered toluene molecule is not shown.
	Fig. 2. Packing diagram of (I)·0.5C7H8, viewed down the b axis, illustrating the alternating layers of aromatic and acetylsulfanyl groups.

(E,E,E)-1,3,5-Tris[4-(acetylsulfanyl)styryl]benzene toluene hemisolvate

Crystal data

C36H30O3S3·0.5C7H8	F(000) = 2744
Mr = 652.85	Dx = 1.293 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 37009 reflections
a = 38.419 (3) Å	θ = 2.2–30.0°
b = 6.8061 (4) Å	µ = 0.26 mm^−1
c = 28.813 (3) Å	T = 122 K
β = 117.115 (12)°	Needle, light-yellow
V = 6706.1 (12) Å^3	0.42 × 0.34 × 0.18 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	9790 independent reflections
Radiation source: fine-focus sealed tube	7824 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω and ϕ scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: numerical via Gaussian integration (Coppens, 1970)	h = −54→54
Tmin = 0.91, Tmax = 0.96	k = −9→9
86319 measured reflections	l = −40→40

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)] = 0.048	Hydrogen site location: difference Fourier map
wR(F^2) = 0.125	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0498P)^2 + 9.7732P] where P = (Fo^2 + 2Fc^2)/3
9790 reflections	(Δ/σ)max = 0.001
442 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.78 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.

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)
S1	0.341115 (15)	−1.20269 (8)	0.478420 (18)	0.04102 (14)
S2	0.067351 (12)	0.52545 (6)	0.041961 (15)	0.02285 (9)
S3	−0.157890 (12)	−1.44589 (7)	0.11078 (2)	0.03233 (11)
O1	0.32139 (4)	−1.4495 (2)	0.39987 (5)	0.0390 (3)
O2	0.04501 (4)	0.2846 (2)	−0.03902 (5)	0.0340 (3)
O3	−0.13039 (4)	−1.70861 (19)	0.06896 (5)	0.0340 (3)
C1	0.11917 (4)	−0.7911 (2)	0.26659 (6)	0.0196 (3)
C2	0.12072 (4)	−0.6043 (2)	0.24710 (6)	0.0202 (3)
C3	0.08726 (4)	−0.5132 (2)	0.20971 (6)	0.0196 (3)
C4	0.05142 (4)	−0.6098 (2)	0.19304 (6)	0.0201 (3)
C5	0.04870 (4)	−0.7959 (2)	0.21147 (6)	0.0193 (3)
C6	0.08306 (4)	−0.8848 (2)	0.24892 (6)	0.0194 (3)
C7	0.15467 (5)	−0.8916 (2)	0.30446 (6)	0.0229 (3)
C8	0.19120 (5)	−0.8298 (3)	0.32038 (7)	0.0276 (3)
C9	0.22711 (5)	−0.9252 (3)	0.35858 (7)	0.0277 (3)
C10	0.22720 (6)	−1.1079 (3)	0.38037 (10)	0.0463 (6)
C11	0.26152 (6)	−1.1923 (3)	0.41686 (10)	0.0475 (6)
C12	0.29679 (5)	−1.0973 (3)	0.43177 (7)	0.0326 (4)
C13	0.29746 (5)	−0.9175 (3)	0.41020 (8)	0.0370 (4)
C14	0.26286 (5)	−0.8316 (3)	0.37425 (8)	0.0335 (4)
C15	0.34492 (5)	−1.4116 (2)	0.44364 (7)	0.0268 (3)
C16	0.38073 (5)	−1.5311 (3)	0.47573 (7)	0.0319 (4)
C17	0.09112 (5)	−0.3226 (2)	0.18819 (6)	0.0219 (3)
C18	0.06363 (5)	−0.2391 (2)	0.14535 (6)	0.0214 (3)
C19	0.06617 (4)	−0.0524 (2)	0.12164 (6)	0.0199 (3)
C20	0.10023 (4)	0.0609 (2)	0.13960 (6)	0.0214 (3)
C21	0.10065 (5)	0.2362 (2)	0.11512 (6)	0.0210 (3)
C22	0.06697 (4)	0.3003 (2)	0.07228 (6)	0.0196 (3)
C23	0.03281 (5)	0.1896 (2)	0.05418 (6)	0.0229 (3)
C24	0.03263 (5)	0.0153 (2)	0.07864 (6)	0.0230 (3)
C25	0.05264 (4)	0.4506 (3)	−0.02391 (6)	0.0245 (3)
C26	0.05066 (5)	0.6206 (3)	−0.05817 (7)	0.0355 (4)
C27	0.01014 (4)	−0.8903 (2)	0.18975 (6)	0.0211 (3)
C28	0.00262 (4)	−1.0798 (2)	0.19309 (6)	0.0207 (3)
C29	−0.03654 (4)	−1.1694 (2)	0.17043 (6)	0.0197 (3)
C30	−0.07046 (5)	−1.0693 (2)	0.13618 (6)	0.0238 (3)
C31	−0.10679 (5)	−1.1580 (2)	0.11723 (6)	0.0253 (3)
C32	−0.11036 (5)	−1.3475 (2)	0.13259 (6)	0.0228 (3)
C33	−0.07718 (5)	−1.4506 (2)	0.16622 (6)	0.0234 (3)
C34	−0.04078 (5)	−1.3625 (2)	0.18385 (6)	0.0223 (3)
C35	−0.15850 (5)	−1.6504 (2)	0.07229 (6)	0.0250 (3)
C36	−0.19844 (5)	−1.7419 (3)	0.04401 (8)	0.0398 (5)
C81	0.27138 (14)	−1.4887 (8)	0.27684 (17)	0.0503 (11)	0.50
C82	0.25164 (18)	−1.3223 (9)	0.2792 (2)	0.0533 (13)	0.50
C83	0.2125 (2)	−1.2977 (19)	0.2439 (3)	0.0538 (19)	0.50
C84	0.19435 (13)	−1.4365 (9)	0.20672 (19)	0.0532 (12)	0.50
C85	0.21379 (14)	−1.6047 (8)	0.20502 (17)	0.0469 (11)	0.50
C86	0.25250 (15)	−1.6323 (7)	0.23968 (17)	0.0457 (10)	0.50
C87	0.2735 (3)	−1.8121 (17)	0.2380 (4)	0.074 (3)	0.50
H2	0.1451	−0.5385	0.2597	0.024*
H4	0.0282	−0.5469	0.1685	0.024*
H6	0.0817	−1.0104	0.2624	0.023*
H7	0.1512	−1.0113	0.3188	0.027*
H8	0.1944	−0.7111	0.3054	0.033*
H10	0.2032	−1.1759	0.3700	0.056*
H11	0.2609	−1.3160	0.4317	0.057*
H13	0.3217	−0.8523	0.4200	0.044*
H14	0.2636	−0.7065	0.3601	0.040*
H17	0.1151	−0.2540	0.2063	0.026*
H18	0.0396	−0.3084	0.1282	0.026*
H20	0.1233	0.0175	0.1688	0.026*
H21	0.1239	0.3122	0.1277	0.025*
H23	0.0097	0.2339	0.0251	0.027*
H24	0.0093	−0.0600	0.0660	0.028*
H27	−0.0118	−0.8076	0.1713	0.025*
H28	0.0243	−1.1638	0.2116	0.025*
H30	−0.0685	−0.9390	0.1258	0.029*
H31	−0.1294	−1.0888	0.0936	0.030*
H33	−0.0794	−1.5799	0.1770	0.028*
H34	−0.0181	−1.4353	0.2057	0.027*
H16A	0.3737	−1.6412	0.4918	0.048*
H16B	0.4002	−1.4484	0.5031	0.048*
H16C	0.3917	−1.5820	0.4533	0.048*
H26A	0.0560	0.7429	−0.0381	0.053*
H26B	0.0245	0.6271	−0.0879	0.053*
H26C	0.0702	0.6030	−0.0709	0.053*
H36A	−0.2125	−1.6827	0.0093	0.060*
H36B	−0.2131	−1.7191	0.0638	0.060*
H36C	−0.1957	−1.8836	0.0405	0.060*
H81	0.2982	−1.5048	0.3009	0.060*	0.50
H82	0.2648	−1.2249	0.3049	0.064*	0.50
H83	0.1985	−1.1852	0.2458	0.065*	0.50
H84	0.1679	−1.4175	0.1815	0.064*	0.50
H85	0.2003	−1.7026	0.1796	0.056*	0.50
H87A	0.3005	−1.8066	0.2656	0.111*	0.50
H87B	0.2734	−1.8214	0.2040	0.111*	0.50
H87C	0.2604	−1.9275	0.2432	0.111*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0297 (2)	0.01860 (17)	0.01911 (17)	−0.00193 (15)	0.01017 (15)	0.00147 (14)
S3	0.02101 (19)	0.0324 (2)	0.0478 (3)	−0.00349 (16)	0.01936 (19)	−0.0109 (2)
S1	0.0366 (3)	0.0421 (3)	0.0269 (2)	0.0170 (2)	−0.00076 (18)	−0.00317 (19)
C19	0.0242 (7)	0.0172 (7)	0.0201 (7)	0.0013 (6)	0.0118 (6)	−0.0006 (5)
C6	0.0233 (7)	0.0184 (7)	0.0174 (6)	−0.0006 (6)	0.0100 (6)	0.0008 (5)
C27	0.0202 (7)	0.0234 (7)	0.0177 (6)	−0.0001 (6)	0.0069 (6)	0.0008 (6)
C3	0.0233 (7)	0.0167 (7)	0.0195 (6)	0.0016 (5)	0.0105 (6)	0.0001 (5)
C29	0.0211 (7)	0.0228 (7)	0.0161 (6)	−0.0017 (6)	0.0093 (5)	−0.0014 (5)
C22	0.0255 (7)	0.0166 (7)	0.0185 (6)	0.0008 (6)	0.0116 (6)	0.0005 (5)
C5	0.0211 (7)	0.0205 (7)	0.0173 (6)	−0.0007 (6)	0.0095 (6)	−0.0017 (5)
C4	0.0204 (7)	0.0200 (7)	0.0186 (6)	0.0017 (6)	0.0077 (6)	0.0008 (5)
O2	0.0369 (7)	0.0403 (7)	0.0264 (6)	−0.0130 (6)	0.0157 (5)	−0.0101 (5)
C2	0.0200 (7)	0.0187 (7)	0.0211 (7)	−0.0005 (5)	0.0088 (6)	0.0009 (6)
O3	0.0299 (6)	0.0294 (7)	0.0444 (7)	−0.0032 (5)	0.0184 (6)	−0.0107 (6)
O1	0.0345 (7)	0.0343 (7)	0.0361 (7)	−0.0006 (6)	0.0055 (6)	−0.0042 (6)
C21	0.0229 (7)	0.0200 (7)	0.0197 (7)	−0.0019 (6)	0.0092 (6)	−0.0018 (6)
C20	0.0215 (7)	0.0221 (7)	0.0182 (6)	0.0023 (6)	0.0070 (6)	0.0002 (6)
C24	0.0215 (7)	0.0227 (7)	0.0222 (7)	−0.0028 (6)	0.0077 (6)	−0.0001 (6)
C1	0.0205 (7)	0.0199 (7)	0.0179 (6)	0.0021 (6)	0.0084 (6)	0.0013 (5)
C7	0.0228 (7)	0.0210 (7)	0.0245 (7)	0.0024 (6)	0.0104 (6)	0.0065 (6)
C18	0.0247 (7)	0.0177 (7)	0.0216 (7)	−0.0013 (6)	0.0105 (6)	−0.0018 (6)
C32	0.0208 (7)	0.0244 (8)	0.0258 (7)	−0.0027 (6)	0.0129 (6)	−0.0062 (6)
C28	0.0199 (7)	0.0255 (7)	0.0168 (6)	0.0002 (6)	0.0085 (6)	0.0017 (6)
C23	0.0207 (7)	0.0243 (8)	0.0211 (7)	0.0013 (6)	0.0073 (6)	0.0026 (6)
C8	0.0238 (8)	0.0239 (8)	0.0339 (9)	0.0031 (6)	0.0122 (7)	0.0099 (7)
C33	0.0263 (7)	0.0226 (7)	0.0235 (7)	−0.0022 (6)	0.0133 (6)	0.0000 (6)
C30	0.0257 (7)	0.0211 (7)	0.0234 (7)	−0.0008 (6)	0.0102 (6)	0.0006 (6)
C17	0.0235 (7)	0.0180 (7)	0.0243 (7)	−0.0001 (6)	0.0109 (6)	0.0005 (6)
C34	0.0226 (7)	0.0234 (7)	0.0200 (7)	0.0000 (6)	0.0088 (6)	0.0007 (6)
C31	0.0213 (7)	0.0253 (8)	0.0261 (8)	0.0024 (6)	0.0079 (6)	−0.0023 (6)
C9	0.0225 (7)	0.0267 (8)	0.0339 (9)	0.0042 (6)	0.0128 (7)	0.0087 (7)
C25	0.0177 (7)	0.0369 (9)	0.0183 (7)	−0.0045 (6)	0.0077 (6)	0.0001 (6)
C15	0.0254 (8)	0.0229 (8)	0.0305 (8)	−0.0001 (6)	0.0112 (7)	0.0057 (6)
C35	0.0221 (7)	0.0240 (8)	0.0255 (7)	−0.0028 (6)	0.0079 (6)	0.0014 (6)
C12	0.0287 (8)	0.0330 (9)	0.0280 (8)	0.0110 (7)	0.0058 (7)	0.0025 (7)
C16	0.0287 (8)	0.0267 (8)	0.0380 (9)	0.0057 (7)	0.0133 (7)	0.0100 (7)
C14	0.0259 (8)	0.0254 (8)	0.0406 (10)	0.0009 (7)	0.0078 (7)	0.0054 (7)
C13	0.0235 (8)	0.0294 (9)	0.0439 (10)	−0.0003 (7)	0.0029 (8)	−0.0025 (8)
C10	0.0230 (8)	0.0407 (11)	0.0703 (15)	0.0046 (8)	0.0169 (9)	0.0299 (11)
C11	0.0341 (10)	0.0434 (12)	0.0631 (14)	0.0123 (9)	0.0206 (10)	0.0320 (11)
C26	0.0308 (9)	0.0514 (12)	0.0224 (8)	−0.0091 (8)	0.0104 (7)	0.0081 (8)
C36	0.0253 (9)	0.0450 (11)	0.0407 (10)	−0.0121 (8)	0.0076 (8)	−0.0057 (9)
C81	0.046 (2)	0.058 (3)	0.036 (2)	−0.007 (2)	0.0094 (19)	0.001 (2)
C82	0.049 (3)	0.060 (3)	0.045 (3)	−0.021 (3)	0.017 (2)	−0.021 (2)
C83	0.033 (3)	0.068 (4)	0.059 (5)	−0.007 (3)	0.019 (3)	−0.019 (4)
C84	0.036 (2)	0.078 (4)	0.046 (2)	−0.008 (2)	0.020 (2)	−0.019 (2)
C85	0.047 (2)	0.059 (3)	0.039 (2)	−0.016 (2)	0.023 (2)	−0.015 (2)
C86	0.059 (3)	0.043 (2)	0.037 (2)	−0.001 (2)	0.024 (2)	0.0047 (18)
C87	0.074 (7)	0.062 (5)	0.077 (7)	0.024 (7)	0.027 (6)	0.022 (6)

Geometric parameters (Å, º)

S2—C22	1.7673 (15)	C8—H8	0.9500
S3—C32	1.7695 (16)	C33—C34	1.388 (2)
S1—C12	1.7706 (18)	C33—H33	0.9500
S1—C15	1.7834 (19)	C30—C31	1.384 (2)
S2—C25	1.7898 (16)	C30—H30	0.9500
S3—C35	1.7731 (18)	C17—H17	0.9500
C19—C24	1.397 (2)	C34—H34	0.9500
C19—C20	1.399 (2)	C31—H31	0.9500
C6—C1	1.396 (2)	C9—C14	1.389 (2)
C6—C5	1.405 (2)	C9—C10	1.393 (3)
C6—H6	0.9500	C25—C26	1.500 (2)
C5—C27	1.468 (2)	C15—C16	1.500 (2)
C27—C28	1.335 (2)	C35—C36	1.506 (2)
C28—C29	1.472 (2)	C12—C13	1.378 (3)
C27—H27	0.9500	C12—C11	1.381 (3)
C3—C2	1.391 (2)	C16—H16A	0.9800
C3—C4	1.399 (2)	C16—H16B	0.9800
C3—C17	1.474 (2)	C16—H16C	0.9800
C17—C18	1.332 (2)	C14—C13	1.388 (2)
C18—C19	1.467 (2)	C14—H14	0.9500
C29—C34	1.400 (2)	C13—H13	0.9500
C29—C30	1.401 (2)	C10—C11	1.382 (3)
C22—C21	1.390 (2)	C10—H10	0.9500
C22—C23	1.392 (2)	C11—H11	0.9500
C5—C4	1.396 (2)	C26—H26A	0.9800
C4—H4	0.9500	C26—H26B	0.9800
O2—C25	1.198 (2)	C26—H26C	0.9800
C2—C1	1.402 (2)	C36—H36A	0.9800
C2—H2	0.9500	C36—H36B	0.9800
O3—C35	1.195 (2)	C36—H36C	0.9800
O1—C15	1.198 (2)	C81—C86	1.386 (7)
C21—C20	1.390 (2)	C81—C82	1.382 (8)
C21—H21	0.9500	C81—H81	0.9500
C20—H20	0.9500	C82—C83	1.390 (8)
C24—C23	1.382 (2)	C82—H82	0.9500
C24—H24	0.9500	C83—C84	1.359 (11)
C1—C7	1.471 (2)	C83—H83	0.9500
C7—C8	1.331 (2)	C84—C85	1.380 (7)
C8—C9	1.467 (2)	C84—H84	0.9500
C7—H7	0.9500	C85—C86	1.375 (7)
C18—H18	0.9500	C85—H85	0.9500
C32—C33	1.389 (2)	C86—C87	1.478 (12)
C32—C31	1.391 (2)	C87—H87A	0.9800
C28—H28	0.9500	C87—H87B	0.9800
C23—H23	0.9500	C87—H87C	0.9800
C22—S2—C25	101.98 (8)	C30—C31—C32	120.44 (15)
C32—S3—C35	103.68 (8)	C30—C31—H31	119.8
C12—S1—C15	101.14 (9)	C32—C31—H31	119.8
C24—C19—C20	118.39 (14)	C14—C9—C10	117.65 (16)
C24—C19—C18	117.92 (14)	C14—C9—C8	119.57 (16)
C20—C19—C18	123.69 (14)	C10—C9—C8	122.79 (16)
C1—C6—C5	120.87 (14)	O2—C25—C26	123.89 (15)
C1—C6—H6	119.6	O2—C25—S2	124.09 (13)
C5—C6—H6	119.6	C26—C25—S2	112.02 (13)
C28—C27—C5	126.97 (14)	O1—C15—C16	124.89 (17)
C28—C27—H27	116.5	O1—C15—S1	123.20 (14)
C5—C27—H27	116.5	C16—C15—S1	111.91 (13)
C2—C3—C4	118.30 (14)	O3—C35—C36	123.70 (17)
C2—C3—C17	118.90 (14)	O3—C35—S3	123.78 (13)
C4—C3—C17	122.77 (14)	C36—C35—S3	112.52 (13)
C34—C29—C30	117.56 (14)	C13—C12—C11	119.53 (17)
C34—C29—C28	119.36 (14)	C13—C12—S1	119.53 (15)
C30—C29—C28	123.07 (14)	C11—C12—S1	120.94 (15)
C21—C22—C23	120.01 (14)	C15—C16—H16A	109.5
C21—C22—S2	119.79 (12)	C15—C16—H16B	109.5
C23—C22—S2	120.18 (12)	H16A—C16—H16B	109.5
C4—C5—C6	118.43 (14)	C15—C16—H16C	109.5
C4—C5—C27	118.08 (13)	H16A—C16—H16C	109.5
C6—C5—C27	123.48 (14)	H16B—C16—H16C	109.5
C5—C4—C3	121.92 (14)	C13—C14—C9	121.18 (17)
C5—C4—H4	119.0	C13—C14—H14	119.4
C3—C4—H4	119.0	C9—C14—H14	119.4
C3—C2—C1	121.43 (14)	C12—C13—C14	120.16 (18)
C3—C2—H2	119.3	C12—C13—H13	119.9
C1—C2—H2	119.3	C14—C13—H13	119.9
C20—C21—C22	119.89 (14)	C11—C10—C9	121.31 (18)
C20—C21—H21	120.1	C11—C10—H10	119.3
C22—C21—H21	120.1	C9—C10—H10	119.3
C21—C20—C19	120.72 (14)	C12—C11—C10	120.15 (19)
C21—C20—H20	119.6	C12—C11—H11	119.9
C19—C20—H20	119.6	C10—C11—H11	119.9
C23—C24—C19	121.22 (15)	C25—C26—H26A	109.5
C23—C24—H24	119.4	C25—C26—H26B	109.5
C19—C24—H24	119.4	H26A—C26—H26B	109.5
C6—C1—C2	119.01 (14)	C25—C26—H26C	109.5
C6—C1—C7	119.31 (14)	H26A—C26—H26C	109.5
C2—C1—C7	121.67 (14)	H26B—C26—H26C	109.5
C8—C7—C1	125.76 (15)	C35—C36—H36A	109.5
C8—C7—H7	117.1	C35—C36—H36B	109.5
C1—C7—H7	117.1	H36A—C36—H36B	109.5
C17—C18—C19	127.49 (15)	C35—C36—H36C	109.5
C17—C18—H18	116.3	H36A—C36—H36C	109.5
C19—C18—H18	116.3	H36B—C36—H36C	109.5
C33—C32—C31	119.87 (15)	C86—C81—C82	120.7 (5)
C33—C32—S3	121.80 (13)	C86—C81—H81	119.7
C31—C32—S3	118.26 (12)	C82—C81—H81	119.7
C27—C28—C29	125.39 (15)	C81—C82—C83	119.9 (7)
C27—C28—H28	117.3	C81—C82—H82	120.1
C29—C28—H28	117.3	C83—C82—H82	120.1
C24—C23—C22	119.77 (14)	C84—C83—C82	119.2 (9)
C24—C23—H23	120.1	C84—C83—H83	120.4
C22—C23—H23	120.1	C82—C83—H83	120.4
C7—C8—C9	127.04 (16)	C83—C84—C85	120.9 (6)
C7—C8—H8	116.5	C83—C84—H84	119.5
C9—C8—H8	116.5	C85—C84—H84	119.5
C34—C33—C32	119.25 (15)	C86—C85—C84	120.7 (4)
C34—C33—H33	120.4	C86—C85—H85	119.6
C32—C33—H33	120.4	C84—C85—H85	119.6
C31—C30—C29	120.87 (15)	C85—C86—C81	118.5 (5)
C31—C30—H30	119.6	C85—C86—C87	121.0 (6)
C29—C30—H30	119.6	C81—C86—C87	120.5 (5)
C18—C17—C3	125.20 (15)	C86—C87—H87A	109.5
C18—C17—H17	117.4	C86—C87—H87B	109.5
C3—C17—H17	117.4	H87A—C87—H87B	109.5
C33—C34—C29	121.94 (15)	C86—C87—H87C	109.5
C33—C34—H34	119.0	H87A—C87—H87C	109.5
C29—C34—H34	119.0	H87B—C87—H87C	109.5
C15—S1—C12—C11	67.1 (2)	C34—C29—C30—C31	1.1 (2)
C25—S2—C22—C21	123.26 (13)	C28—C29—C30—C31	−177.90 (14)
C35—S3—C32—C31	117.27 (13)	C19—C18—C17—C3	−178.64 (14)
C25—S2—C22—C23	−58.35 (14)	C2—C3—C17—C18	165.27 (16)
C1—C6—C5—C4	−1.2 (2)	C4—C3—C17—C18	−12.8 (2)
C1—C6—C5—C27	177.37 (14)	C32—C33—C34—C29	2.6 (2)
C28—C27—C5—C4	163.98 (15)	C30—C29—C34—C33	−3.0 (2)
C28—C27—C5—C6	−14.6 (2)	C28—C29—C34—C33	176.08 (14)
C6—C5—C4—C3	1.8 (2)	C29—C30—C31—C32	1.1 (2)
C27—C5—C4—C3	−176.87 (14)	C33—C32—C31—C30	−1.5 (2)
C2—C3—C4—C5	−2.2 (2)	S3—C32—C31—C30	175.46 (13)
C17—C3—C4—C5	175.83 (14)	C7—C8—C9—C14	−174.32 (19)
C4—C3—C2—C1	2.2 (2)	C7—C8—C9—C10	5.6 (3)
C17—C3—C2—C1	−175.99 (14)	C22—S2—C25—O2	0.34 (17)
C23—C22—C21—C20	0.5 (2)	C22—S2—C25—C26	179.87 (12)
S2—C22—C21—C20	178.87 (12)	C12—S1—C15—O1	0.86 (18)
C22—C21—C20—C19	−0.1 (2)	C12—S1—C15—C16	−179.14 (13)
C24—C19—C20—C21	−0.1 (2)	C32—S3—C35—O3	6.96 (18)
C18—C19—C20—C21	179.70 (14)	C32—S3—C35—C36	−172.73 (13)
C20—C19—C24—C23	0.0 (2)	C15—S1—C12—C13	−113.17 (17)
C18—C19—C24—C23	−179.85 (14)	C10—C9—C14—C13	0.3 (3)
C5—C6—C1—C2	1.1 (2)	C8—C9—C14—C13	−179.82 (18)
C5—C6—C1—C7	−177.91 (14)	C11—C12—C13—C14	0.8 (3)
C3—C2—C1—C6	−1.6 (2)	S1—C12—C13—C14	−178.90 (16)
C3—C2—C1—C7	177.38 (14)	C9—C14—C13—C12	−1.1 (3)
C6—C1—C7—C8	172.41 (16)	C14—C9—C10—C11	0.9 (3)
C2—C1—C7—C8	−6.6 (3)	C8—C9—C10—C11	−179.0 (2)
C24—C19—C18—C17	−175.28 (16)	C13—C12—C11—C10	0.3 (4)
C20—C19—C18—C17	4.9 (3)	S1—C12—C11—C10	−179.97 (19)
C35—S3—C32—C33	−65.81 (15)	C9—C10—C11—C12	−1.2 (4)
C5—C27—C28—C29	−179.57 (14)	C86—C81—C82—C83	−0.2 (10)
C34—C29—C28—C27	−169.74 (15)	C81—C82—C83—C84	−1.5 (13)
C30—C29—C28—C27	9.3 (2)	C82—C83—C84—C85	2.9 (13)
C19—C24—C23—C22	0.4 (2)	C83—C84—C85—C86	−2.7 (9)
C21—C22—C23—C24	−0.6 (2)	C84—C85—C86—C81	0.9 (7)
S2—C22—C23—C24	−179.00 (12)	C84—C85—C86—C87	−179.9 (6)
C1—C7—C8—C9	179.06 (16)	C82—C81—C86—C85	0.5 (7)
C31—C32—C33—C34	−0.3 (2)	C82—C81—C86—C87	−178.7 (6)
S3—C32—C33—C34	−177.15 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···O3^i	0.98	2.52	3.403 (2)	150
C16—H16B···O2^ii	0.98	2.46	3.368 (2)	155
C24—H24···O2^iii	0.95	2.41	3.356 (2)	173
C26—H26C···O3^iv	0.98	2.40	3.272 (2)	148
C81—H81···O1	0.95	2.60	3.181 (5)	120

Symmetry codes: (i) x+1/2, −y−7/2, z+1/2; (ii) −x+1/2, y−3/2, −z+1/2; (iii) −x, −y, −z; (iv) −x, −y−1, −z.