Synthesis and photophysical properties of 2,5,8,11-tetra­kis­(5-hexyl­thio­phen-2-yl)tetra­thieno[2,3-a:3',2'-c:2'',3''-f:3''',2'''-h]naphthalene

The title compound, C₅₈H₆₄S₈, has been prepared by Pd-catalysed direct C-H aryl­ation of tetra­thieno­naphthalene (TTN) with 5-hexyl-2-iodo­thio­phene and recrystallized by slow evaporation from di­chloro­methane. The crystal structure shows a completely planar geometry of the TTN core, crystallizing in the monoclinic space group P2₁/c. The structure consists of slipped [pi]-stacks and the inter­facial distance between the mean planes of the TTN cores is 3.456 (5) Å, which is slightly larger than that of the comparable derivative of tetra­thieno­anthracene (TTA) with 2-hexyl­thio­phene groups. The packing in the two structures is greatly influenced by both the aromatic core of the structure and the alkyl side chains.

S1. Comment

Fused-sulfur heteroarenes have been well investigated due to their potential applications in organic optoelectronic materials and devices (Murphy & Fréchet, 2007; Mishra et al., 2009). New synthetic methodologies and novel structures have been developed and significant effort has been devoted to the investigation of the relationship between their special intrinsic properties and their structures. Optimisation of the properties of this type of conjugated system in optoelectric devices involves maximizing π-orbital overlap by reducing the freedom of rotation in the oligomers and possibly inducing a densely packed crystal structure with face-to-face π-stacking motifs. Recently, divinylbenzene, naphthalene, anthracene, tetracene etc. (Didane et al., 2008; Kim et al., 2007; Meng et al., 2005; Merlo et al., 2005) have been successfully introduced into oligothiophenes to form fused thiophene derivatives, which have provided excellent stable semiconductor materials with relatively high band-gap energies and low-lying highest occupied molecular orbitals (E_HOMO; HOMO is the highest occupied molecular orbital). Single-crystal X-ray diffraction studies of these fused thiophene derivatives have provided some understanding of the relationship between the π-stacking interactions and the performance of the corresponding thin-film optoelectronic devices (Coropceanu et al., 2007; Sheraw et al., 2003). In this paper, we present the synthesis, characterization, crystal structure and photophysical properties of the title compound, (I)

Compound (I) was synthesized by Pd-catalyzed direct C—H arylation of tetrathienonaphthalene (TTN) using 5-hexyl-2-iodothiophene, and the crude product was purified by silica-gel column chromatography (1:1 hexane–CH₂Cl₂, R_F = 0.55) to afford pure (I) in 34% yield as a pale-yellow solid. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a solution in CH₂Cl₂.

Compound (I) crystallizes in the monoclinic space group P2₁/c with two molecules in the unit cell. The molecular structure of (I) (Fig. 1) has inversion symmetry. The crystals of (I) are composed of relatively closely spaced continuous stacks of planar molecules, each slipped relative to its neighbours by a unit-cell translation along b. The distance between the nearest-neighbour planes is 3.456 (5) Å. The closest C···C intra-stack contact between atom C3 of the fused thiophene ring and atom C14 of the substituent thiophene ring per nearest-neighbour pair within a stack is 3.616 (5) Å, which is slightly longer than twice the van der Waals radius (Bondi, 1964). Also of note is that there are a number of S···C interactions [the shortest being 3.595 (4) Å between atoms S1 and C9(x, y - 1, z)] along the slipped π-stacks.

It is interesting to compare the crystal structure of (I) with that of the analogous tetrahexylthiophene-substituted tetrathienoanthracene (TTA), (II), which posesses an additional annulated phenyl group in the central skeleton (Leitch et al. 2012). Both structures crystallize in the monoclinic space group and slight propeller-like distortions were observed between the central tetrathiophene aromatic core and the hexylthiophene groups by rotation about the connecting C—C bonds. The dihedral angles between the two unique thiophene groups (defined as S3/C10/C7/C6 and S4/C14/C9/C6) are 10.9 (6) and 13.1 (5)°. respectively, for (I) [the corresponding values in (II) are 6.7 and 2.8 (3)°]. Furthermore, the packing of the molecules of (I) and (II) seems to be greatly affected by the hexyl chains. As is apparent from Figs. 3 and 4, the hexyl substituents in both compounds form an interdigitated network along the herringbone array. Two of the hexyl side chains in the molecule of (I) adopt an ordered extended conformation, while the other two hexyl chains adopt disordered folded conformations. In comparison, only the terminal C atoms of the hexyl chains in (II) are folded. The different fused-ring systems of (I) and (II), with the hexyl side chains inclining towards the available space, results in different interlayer distances, which are slightly larger in (I) than in (II) [distance between molecular planes is about 3.41 Å in (II) versus 3.456 (5) Å in (I)]. This result presumably reflects the stronger π-stacking for the more extended planar aromatic core in (II).

The organization of the stacks relative to each other differs between the two compounds (Figs. 3 and 4). In (II), there are elements of five stacks in the conventional unit cell, with the molecular planes of adjacent stacks tilted by about 89° relative to each other. In contrast, there are parts of six stacks in the unit cell of (II), with the molecular planes in the central stack inclined by 65.28 (8)° relative to those of its neighbours in (I) (see Fig. 2). Given the similarity in the intra-stack geometry and the differences in the inter-stack geometry, it is reasonable to conclude that the π-stacking is greatly affected by the aromatic core of the structures and the alkyl chains. These factors should be considered during the investigation of other conjugated compounds as optelectronic materials.

The UV–Vis absorption and fluorescence spectra for (I) in CH₂Cl₂ are presented in Fig. 5. The strongest absorption band is observed at 388 nm and an obscure shoulder band is observed at 425 nm, which was assigned to the four-directional π-extension of hexylthiophene. In the fluorescence spectrum in CH₂Cl₂, compound (I) shows a structured emission with a maximum at 456 nm.

Related literature

For related literature, see: Bondi (1964); Coropceanu et al. (2007); Didane et al. (2008); Kim et al. (2007); Leitch et al. (2012); Meng et al. (2005); Merlo et al. (2005); Mishra et al. (2009); Murphy & Fréchet (2007); Sheraw et al. (2003).

S2. Experimental

A 20 ml glass vessel equipped with a J. Young O-ring tap containing a magnetic stirring bar was flame-dried under vacuum and filled with argon. After cooling to room temperature, PdCl₂ (8.8 mg, 50 mmol), 2,2'-bipyridyl (16 mg, 100 mmol), AgCO₃(276 mg, 1 mmol) and dry m-xylene (1 ml) were added. The vessel was heated at 333 K for 20 min. To this vessel were added tetrathienonaphthalene (TTN) (70 mg, 0.198 mmol), 5-hexyl-2-iodothiophene (465 mg, 1.5 mmol) and m-xylene (2 ml) under argon. The vessel was sealed with the O-ring tap and heated at 393 K for 36 h. After cooling, the mixture was filtered and the solvent was removed by rotary evaporation. The crude product was purified through a silica-gel column (hexanes–CH₂Cl₂, 3:1 v/v, as eluent) to afford the final product, (I), as a light-yellow solid (yield 68.5 mg, 34%; decomposition >473 K). Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a solution in CH₂Cl₂.

Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 8.06 (4H, s), 7.05 (4H, d, J = 3.0 Hz), 6.45 (4H, d, J = 3.2 Hz), 2.72 (8H, t, J = 7.3 Hz), 1.74 (8H, m, J = 7.2 Hz), 1.50–1.30 (24H, m), 0.98 (12H, t, J = 7.3 Hz); ¹³C NMR (CDCl₃, δ, p.p.m.): 138.1, 137.4, 134.8, 133.9, 133.6, 131.1, 127.1, 122.9, 120.7, 31.6, 31.7, 31.0, 29.1, 22.8, 14.4; UV–Vis: 240 (ε_max = 72262 M^-1 cm^-1), 206 (ε_max = 62762 M^-1 cm^-1). Analysis, calculated for C₅₈H₆₄S₈: C 68.46, H 6.34, S 25.20%; found: C 68.39, H 6.70, N 25.11%.

S3. Refinement

The structure solution revealed positional disorder for one of the alkyl chains. The disordered fragments are located on general positions and are not related by any symmetry elements. Occupancy factors for the disordered fragments were successfully modelled in a ratio of 0.66:0.34 with stable refinement results. The positions of all H atoms were obtained from Fourier map analysis; subsequently, all H atoms were treated as idealized contributions, with C—H = 0.95–0.99 Å and U_iso(H) = 1.5U_eq(C) for methyl H or 1.2U_eq(C) for all others. [Added text OK?]

Computing details

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear (Rigaku, 1999); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A perspective view of (I), showing the partial atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.
	Fig. 2. Slipped π-stack drawings of (I) (top) and (II) (bottom). In the π-stacked structures, the hexyl chains have been omitted for clarity.
	Fig. 3. A partial packing diagram for (I). H atoms have been omitted for clarity. [Please revise; some white text can be seen across the middle and in the top and bottom right-hand corners]
	Fig. 4. A partial packing diagram for (II) (Leitch et al.,2012). H atoms have been omitted for clarity. [Please revise; some white text can be seen in two places across the middle]
	Fig. 5. UV–Vis absorption and fluorescence spectra for (I) in CH2Cl2.

2,5,8,11-Tetrakis(5-hexylthiophen-2-yl)tetrathieno[2,3-a:3',2'-c:2'',3''-f:3''',2'''-h]naphthalene

Crystal data

C58H64S8	F(000) = 1080
Mr = 1017.57	Dx = 1.305 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
a = 16.735 (4) Å	Cell parameters from 5511 reflections
b = 6.4066 (17) Å	θ = 3.0–27.5°
c = 24.197 (6) Å	µ = 0.38 mm^−1
β = 93.0512 (11)°	T = 123 K
V = 2590.5 (12) Å^3	Prism, yellow
Z = 2	0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Saturn70 CCD area-detector diffractometer	5895 independent reflections
Radiation source: fine-focus sealed tube	4651 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ϕ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan ?	h = −21→21
Tmin = 0.927, Tmax = 0.927	k = −7→8
19592 measured reflections	l = −31→30

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.184	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0732P)^2 + 3.5983P] where P = (Fo^2 + 2Fc^2)/3
5895 reflections	(Δ/σ)max < 0.001
317 parameters	Δρmax = 0.83 e Å^−3
81 restraints	Δρmin = −0.64 e Å^−3

Special details

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. 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 > 2sigma(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)
C1	0.02022 (19)	0.9074 (5)	0.01021 (14)	0.0263 (7)
C2	0.09638 (19)	0.8606 (5)	−0.01128 (14)	0.0253 (7)
C3	0.1323 (2)	0.9842 (5)	−0.05026 (14)	0.0270 (7)
C4	0.09189 (19)	1.1660 (5)	−0.07064 (14)	0.0279 (7)
C5	0.01725 (19)	1.2148 (5)	−0.05066 (14)	0.0252 (7)
C6	0.2071 (2)	0.9042 (5)	−0.06569 (14)	0.0285 (7)
H1	0.2394	0.9703	−0.0916	0.034*
C7	0.22759 (19)	0.7214 (5)	−0.03915 (15)	0.0287 (7)
C8	0.1162 (2)	1.3086 (5)	−0.11078 (14)	0.0275 (7)
H2	0.1655	1.2970	−0.1282	0.033*
C9	0.06220 (19)	1.4656 (5)	−0.12244 (14)	0.0267 (7)
C10	0.2992 (2)	0.5953 (6)	−0.04533 (16)	0.0315 (8)
C11	0.3160 (2)	0.3987 (6)	−0.02595 (17)	0.0369 (9)
H3	0.2804	0.3194	−0.0050	0.044*
C12	0.3918 (2)	0.3259 (7)	−0.04022 (18)	0.0424 (10)
H4	0.4117	0.1915	−0.0302	0.051*
C13	0.4331 (2)	0.4634 (6)	−0.06919 (17)	0.0366 (9)
C14	0.06748 (19)	1.6356 (5)	−0.16130 (14)	0.0278 (7)
C15	0.0243 (2)	1.8176 (5)	−0.16603 (15)	0.0301 (8)
H5	−0.0180	1.8514	−0.1430	0.036*
C16	0.0491 (2)	1.9490 (6)	−0.20842 (15)	0.0328 (8)
H6	0.0245	2.0795	−0.2170	0.039*
C17	0.1117 (2)	1.8716 (6)	−0.23616 (16)	0.0361 (8)
C18	0.5145 (2)	0.4452 (7)	−0.09313 (18)	0.0425 (10)
H7	0.5490	0.5603	−0.0785	0.051*
H8	0.5084	0.4616	−0.1338	0.051*
C19	0.5557 (2)	0.2381 (6)	−0.07985 (17)	0.0403 (9)
H9	0.5208	0.1224	−0.0936	0.048*
H10	0.5637	0.2233	−0.0392	0.048*
C20	0.6365 (2)	0.2218 (6)	−0.10599 (17)	0.0377 (9)
H11	0.6279	0.2275	−0.1468	0.045*
H12	0.6697	0.3435	−0.0943	0.045*
C21	0.6816 (2)	0.0238 (6)	−0.09038 (17)	0.0379 (9)
H13	0.6463	−0.0973	−0.0989	0.046*
H14	0.6942	0.0243	−0.0499	0.046*
C22	0.7592 (2)	−0.0054 (6)	−0.11977 (17)	0.0387 (9)
H15	0.7465	−0.0231	−0.1599	0.046*
H16	0.7924	0.1218	−0.1147	0.046*
C23	0.8067 (2)	−0.1929 (7)	−0.09816 (17)	0.0406 (9)
H17	0.8230	−0.1713	−0.0591	0.061*
H18	0.8544	−0.2101	−0.1195	0.061*
H19	0.7735	−0.3186	−0.1019	0.061*
C24	0.1549 (3)	1.9680 (8)	−0.28250 (18)	0.0504 (12)	0.654 (6)
H20	0.1317	2.1074	−0.2908	0.060*	0.654 (6)
H21	0.1461	1.8806	−0.3160	0.060*	0.654 (6)
C25	0.2472 (6)	1.9921 (19)	−0.2694 (6)	0.046 (2)	0.654 (6)
H22	0.2712	1.8509	−0.2698	0.056*	0.654 (6)
H23	0.2694	2.0712	−0.3002	0.056*	0.654 (6)
C26	0.2755 (6)	2.095 (2)	−0.2167 (3)	0.050 (2)	0.654 (6)
H24	0.2497	2.0232	−0.1862	0.060*	0.654 (6)
H25	0.2549	2.2402	−0.2178	0.060*	0.654 (6)
C27	0.3638 (5)	2.1064 (12)	−0.2013 (3)	0.061 (2)	0.654 (6)
H26	0.3855	1.9630	−0.1978	0.073*	0.654 (6)
H27	0.3719	2.1753	−0.1648	0.073*	0.654 (6)
C28	0.4112 (6)	2.2296 (15)	−0.2450 (4)	0.092 (3)	0.654 (6)
H28	0.3958	2.1835	−0.2831	0.110*	0.654 (6)
H29	0.4697	2.2127	−0.2381	0.110*	0.654 (6)
C29	0.3836 (6)	2.4694 (13)	−0.2346 (5)	0.091 (3)	0.654 (6)
H30	0.3285	2.4889	−0.2494	0.136*	0.654 (6)
H31	0.4191	2.5647	−0.2534	0.136*	0.654 (6)
H32	0.3867	2.4990	−0.1948	0.136*	0.654 (6)
C24A	0.1549 (3)	1.9680 (8)	−0.28250 (18)	0.0504 (12)	0.35
H33	0.1422	2.1189	−0.2839	0.060*	0.346 (6)
H34	0.1339	1.9055	−0.3178	0.060*	0.346 (6)
C25A	0.2441 (11)	1.943 (4)	−0.2786 (12)	0.046 (2)	0.35
H35	0.2674	1.9727	−0.3146	0.056*	0.346 (6)
H36	0.2596	1.8005	−0.2665	0.056*	0.346 (6)
C26A	0.2706 (12)	2.105 (4)	−0.2352 (7)	0.050 (2)	0.35
H37	0.2467	2.0786	−0.1993	0.060*	0.346 (6)
H38	0.2580	2.2488	−0.2477	0.060*	0.346 (6)
C27A	0.3617 (9)	2.062 (2)	−0.2323 (7)	0.061 (2)	0.35
H39	0.3745	1.9383	−0.2089	0.073*	0.346 (6)
H40	0.3806	2.0360	−0.2698	0.073*	0.346 (6)
C28A	0.4019 (12)	2.258 (3)	−0.2069 (7)	0.092 (3)	0.35
H41	0.4530	2.2232	−0.1866	0.110*	0.346 (6)
H42	0.3663	2.3296	−0.1815	0.110*	0.346 (6)
C29A	0.4170 (12)	2.403 (3)	−0.2618 (9)	0.091 (3)	0.35
H43	0.4315	2.3131	−0.2925	0.136*	0.346 (6)
H44	0.4605	2.5020	−0.2530	0.136*	0.346 (6)
H45	0.3680	2.4799	−0.2725	0.136*	0.346 (6)
S1	0.15609 (5)	0.64473 (14)	0.00601 (4)	0.0286 (2)
S2	−0.02097 (5)	1.43983 (14)	−0.08278 (4)	0.0291 (2)
S3	0.37798 (6)	0.68961 (16)	−0.08098 (5)	0.0415 (3)
S4	0.13978 (6)	1.62914 (16)	−0.21012 (4)	0.0368 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0212 (15)	0.0249 (17)	0.0328 (18)	0.0026 (13)	0.0013 (13)	−0.0064 (14)
C2	0.0221 (15)	0.0230 (17)	0.0308 (17)	0.0051 (13)	0.0011 (13)	−0.0037 (14)
C3	0.0250 (16)	0.0235 (17)	0.0327 (18)	0.0052 (13)	0.0038 (13)	−0.0034 (14)
C4	0.0239 (16)	0.0274 (18)	0.0325 (18)	0.0021 (13)	0.0033 (13)	−0.0077 (14)
C5	0.0221 (15)	0.0214 (16)	0.0320 (17)	0.0044 (13)	0.0021 (13)	−0.0050 (14)
C6	0.0255 (16)	0.0291 (18)	0.0313 (18)	0.0032 (14)	0.0053 (13)	−0.0035 (14)
C7	0.0220 (15)	0.0292 (18)	0.0356 (18)	0.0061 (14)	0.0072 (13)	−0.0025 (15)
C8	0.0243 (16)	0.0285 (18)	0.0300 (17)	0.0055 (14)	0.0038 (13)	−0.0037 (14)
C9	0.0225 (15)	0.0269 (17)	0.0311 (17)	0.0003 (13)	0.0055 (13)	−0.0034 (14)
C10	0.0202 (15)	0.035 (2)	0.040 (2)	0.0078 (14)	0.0083 (14)	−0.0018 (16)
C11	0.0258 (17)	0.036 (2)	0.050 (2)	0.0060 (16)	0.0143 (16)	0.0047 (18)
C12	0.0315 (19)	0.043 (2)	0.054 (3)	0.0124 (17)	0.0137 (18)	0.006 (2)
C13	0.0246 (17)	0.038 (2)	0.048 (2)	0.0101 (16)	0.0083 (15)	−0.0003 (18)
C14	0.0247 (16)	0.0301 (18)	0.0285 (17)	0.0034 (14)	0.0016 (13)	−0.0035 (14)
C15	0.0281 (17)	0.0292 (18)	0.0334 (18)	0.0009 (14)	0.0051 (14)	−0.0008 (15)
C16	0.0297 (18)	0.0302 (19)	0.038 (2)	0.0058 (15)	−0.0034 (15)	−0.0001 (16)
C17	0.0340 (19)	0.042 (2)	0.0323 (19)	0.0057 (17)	0.0005 (15)	0.0056 (17)
C18	0.0294 (19)	0.043 (2)	0.057 (3)	0.0119 (17)	0.0160 (17)	0.010 (2)
C19	0.0285 (18)	0.043 (2)	0.050 (2)	0.0107 (17)	0.0141 (17)	0.0057 (19)
C20	0.0246 (17)	0.042 (2)	0.048 (2)	0.0093 (16)	0.0117 (16)	0.0041 (18)
C21	0.0261 (18)	0.043 (2)	0.045 (2)	0.0087 (16)	0.0091 (16)	0.0027 (18)
C22	0.0307 (19)	0.042 (2)	0.045 (2)	0.0090 (17)	0.0085 (16)	−0.0040 (18)
C23	0.0281 (18)	0.046 (2)	0.048 (2)	0.0101 (17)	0.0077 (16)	−0.0079 (19)
C24	0.052 (2)	0.060 (3)	0.041 (2)	0.010 (2)	0.0135 (19)	0.012 (2)
C25	0.048 (3)	0.048 (6)	0.045 (5)	0.019 (3)	0.020 (3)	0.010 (4)
C26	0.046 (3)	0.063 (3)	0.043 (5)	−0.007 (2)	0.014 (4)	0.007 (4)
C27	0.066 (4)	0.054 (4)	0.062 (4)	−0.008 (3)	−0.013 (4)	−0.002 (4)
C28	0.067 (4)	0.118 (6)	0.091 (6)	−0.012 (4)	0.011 (4)	−0.019 (5)
C29	0.078 (5)	0.090 (5)	0.104 (6)	−0.007 (4)	−0.005 (4)	0.025 (5)
C24A	0.052 (2)	0.060 (3)	0.041 (2)	0.010 (2)	0.0135 (19)	0.012 (2)
C25A	0.048 (3)	0.048 (6)	0.045 (5)	0.019 (3)	0.020 (3)	0.010 (4)
C26A	0.046 (3)	0.063 (3)	0.043 (5)	−0.007 (2)	0.014 (4)	0.007 (4)
C27A	0.066 (4)	0.054 (4)	0.062 (4)	−0.008 (3)	−0.013 (4)	−0.002 (4)
C28A	0.067 (4)	0.118 (6)	0.091 (6)	−0.012 (4)	0.011 (4)	−0.019 (5)
C29A	0.078 (5)	0.090 (5)	0.104 (6)	−0.007 (4)	−0.005 (4)	0.025 (5)
S1	0.0225 (4)	0.0276 (5)	0.0361 (5)	0.0060 (3)	0.0064 (3)	−0.0010 (4)
S2	0.0234 (4)	0.0288 (5)	0.0355 (5)	0.0057 (3)	0.0047 (3)	0.0008 (4)
S3	0.0303 (5)	0.0390 (6)	0.0569 (6)	0.0116 (4)	0.0188 (4)	0.0111 (5)
S4	0.0352 (5)	0.0410 (6)	0.0351 (5)	0.0118 (4)	0.0089 (4)	0.0042 (4)

Geometric parameters (Å, º)

C1—C5^i	1.425 (5)	C20—H12	0.9900
C1—C2	1.434 (4)	C21—C22	1.525 (5)
C1—C1^i	1.440 (7)	C21—H13	0.9900
C2—C3	1.393 (5)	C21—H14	0.9900
C2—S1	1.744 (3)	C22—C23	1.519 (5)
C3—C6	1.420 (4)	C22—H15	0.9900
C3—C4	1.422 (5)	C22—H16	0.9900
C4—C5	1.399 (4)	C23—H17	0.9800
C4—C8	1.409 (5)	C23—H18	0.9800
C5—C1^i	1.425 (5)	C23—H19	0.9800
C5—S2	1.743 (3)	C24—C25	1.569 (12)
C6—C7	1.370 (5)	C24—H20	0.9900
C6—H1	0.9500	C24—H21	0.9900
C7—C10	1.459 (4)	C25—C26	1.491 (13)
C7—S1	1.734 (3)	C25—H22	0.9900
C8—C9	1.371 (5)	C25—H23	0.9900
C8—H2	0.9500	C26—C27	1.507 (12)
C9—C14	1.445 (5)	C26—H24	0.9900
C9—S2	1.740 (3)	C26—H25	0.9900
C10—C11	1.368 (5)	C27—C28	1.568 (8)
C10—S3	1.723 (4)	C27—H26	0.9900
C11—C12	1.411 (5)	C27—H27	0.9900
C11—H3	0.9500	C28—C29	1.627 (8)
C12—C13	1.340 (6)	C28—H28	0.9900
C12—H4	0.9500	C28—H29	0.9900
C13—C18	1.513 (5)	C29—H30	0.9800
C13—S3	1.733 (4)	C29—H31	0.9800
C14—C15	1.373 (5)	C29—H32	0.9800
C14—S4	1.736 (3)	C25A—C26A	1.524 (18)
C15—C16	1.406 (5)	C25A—H35	0.9900
C15—H5	0.9500	C25A—H36	0.9900
C16—C17	1.367 (5)	C26A—C27A	1.547 (18)
C16—H6	0.9500	C26A—H37	0.9900
C17—C24	1.498 (5)	C26A—H38	0.9900
C17—S4	1.732 (4)	C27A—C28A	1.538 (10)
C18—C19	1.522 (5)	C27A—H39	0.9900
C18—H7	0.9900	C27A—H40	0.9900
C18—H8	0.9900	C28A—C29A	1.651 (17)
C19—C20	1.527 (5)	C28A—H41	0.9900
C19—H9	0.9900	C28A—H42	0.9900
C19—H10	0.9900	C29A—H43	0.9800
C20—C21	1.514 (5)	C29A—H44	0.9800
C20—H11	0.9900	C29A—H45	0.9800
C5^i—C1—C2	124.5 (3)	H13—C21—H14	107.6
C5^i—C1—C1^i	118.2 (4)	C23—C22—C21	112.3 (3)
C2—C1—C1^i	117.3 (4)	C23—C22—H15	109.1
C3—C2—C1	123.5 (3)	C21—C22—H15	109.1
C3—C2—S1	110.5 (2)	C23—C22—H16	109.1
C1—C2—S1	126.0 (3)	C21—C22—H16	109.1
C2—C3—C6	113.0 (3)	H15—C22—H16	107.9
C2—C3—C4	119.0 (3)	C22—C23—H17	109.5
C6—C3—C4	127.9 (3)	C22—C23—H18	109.5
C5—C4—C8	112.9 (3)	H17—C23—H18	109.5
C5—C4—C3	118.7 (3)	C22—C23—H19	109.5
C8—C4—C3	128.3 (3)	H17—C23—H19	109.5
C4—C5—C1^i	123.3 (3)	H18—C23—H19	109.5
C4—C5—S2	110.1 (3)	C17—C24—C25	113.5 (7)
C1^i—C5—S2	126.6 (2)	C17—C24—H20	108.9
C7—C6—C3	112.8 (3)	C25—C24—H20	108.9
C7—C6—H1	123.6	C17—C24—H21	108.9
C3—C6—H1	123.6	C25—C24—H21	108.9
C6—C7—C10	127.7 (3)	H20—C24—H21	107.7
C6—C7—S1	111.9 (2)	C26—C25—C24	118.8 (8)
C10—C7—S1	120.4 (3)	C26—C25—H22	107.6
C9—C8—C4	114.0 (3)	C24—C25—H22	107.6
C9—C8—H2	123.0	C26—C25—H23	107.6
C4—C8—H2	123.0	C24—C25—H23	107.6
C8—C9—C14	128.7 (3)	H22—C25—H23	107.1
C8—C9—S2	110.8 (3)	C25—C26—C27	119.7 (8)
C14—C9—S2	120.6 (2)	C25—C26—H24	107.4
C11—C10—C7	129.1 (3)	C27—C26—H24	107.4
C11—C10—S3	110.2 (2)	C25—C26—H25	107.4
C7—C10—S3	120.8 (3)	C27—C26—H25	107.4
C10—C11—C12	113.1 (3)	H24—C26—H25	106.9
C10—C11—H3	123.5	C26—C27—C28	112.4 (7)
C12—C11—H3	123.5	C26—C27—H26	109.1
C13—C12—C11	113.9 (4)	C28—C27—H26	109.1
C13—C12—H4	123.0	C26—C27—H27	109.1
C11—C12—H4	123.0	C28—C27—H27	109.1
C12—C13—C18	130.5 (4)	H26—C27—H27	107.9
C12—C13—S3	110.6 (3)	C27—C28—C29	102.3 (6)
C18—C13—S3	118.9 (3)	C27—C28—H28	111.3
C15—C14—C9	130.1 (3)	C29—C28—H28	111.3
C15—C14—S4	110.2 (3)	C27—C28—H29	111.3
C9—C14—S4	119.6 (2)	C29—C28—H29	111.3
C14—C15—C16	113.3 (3)	H28—C28—H29	109.2
C14—C15—H5	123.4	C26A—C25A—H35	111.2
C16—C15—H5	123.4	C26A—C25A—H36	111.2
C17—C16—C15	113.9 (3)	H35—C25A—H36	109.1
C17—C16—H6	123.1	C25A—C26A—C27A	99.3 (15)
C15—C16—H6	123.1	C25A—C26A—H37	111.9
C16—C17—C24	129.1 (4)	C27A—C26A—H37	111.9
C16—C17—S4	110.3 (3)	C25A—C26A—H38	111.9
C24—C17—S4	120.7 (3)	C27A—C26A—H38	111.9
C13—C18—C19	113.2 (3)	H37—C26A—H38	109.6
C13—C18—H7	108.9	C28A—C27A—C26A	106.4 (15)
C19—C18—H7	108.9	C28A—C27A—H39	110.5
C13—C18—H8	108.9	C26A—C27A—H39	110.5
C19—C18—H8	108.9	C28A—C27A—H40	110.5
H7—C18—H8	107.8	C26A—C27A—H40	110.5
C18—C19—C20	111.9 (3)	H39—C27A—H40	108.6
C18—C19—H9	109.2	C27A—C28A—C29A	102.7 (10)
C20—C19—H9	109.2	C27A—C28A—H41	111.2
C18—C19—H10	109.2	C29A—C28A—H41	111.2
C20—C19—H10	109.2	C27A—C28A—H42	111.2
H9—C19—H10	107.9	C29A—C28A—H42	111.2
C21—C20—C19	113.2 (3)	H41—C28A—H42	109.1
C21—C20—H11	108.9	C28A—C29A—H43	109.5
C19—C20—H11	108.9	C28A—C29A—H44	109.5
C21—C20—H12	108.9	H43—C29A—H44	109.5
C19—C20—H12	108.9	C28A—C29A—H45	109.5
H11—C20—H12	107.7	H43—C29A—H45	109.5
C20—C21—C22	114.3 (3)	H44—C29A—H45	109.5
C20—C21—H13	108.7	C7—S1—C2	91.71 (16)
C22—C21—H13	108.7	C9—S2—C5	92.23 (16)
C20—C21—H14	108.7	C10—S3—C13	92.24 (18)
C22—C21—H14	108.7	C17—S4—C14	92.36 (17)
C5^i—C1—C2—C3	−179.0 (3)	S2—C9—C14—S4	−166.80 (19)
C1^i—C1—C2—C3	0.1 (6)	C9—C14—C15—C16	178.0 (3)
C5^i—C1—C2—S1	1.9 (5)	S4—C14—C15—C16	0.2 (4)
C1^i—C1—C2—S1	−179.0 (3)	C14—C15—C16—C17	−0.8 (5)
C1—C2—C3—C6	−179.2 (3)	C15—C16—C17—C24	−178.7 (4)
S1—C2—C3—C6	0.0 (4)	C15—C16—C17—S4	1.0 (4)
C1—C2—C3—C4	−0.6 (5)	C12—C13—C18—C19	−2.2 (7)
S1—C2—C3—C4	178.6 (3)	S3—C13—C18—C19	−179.6 (3)
C2—C3—C4—C5	0.2 (5)	C13—C18—C19—C20	178.3 (4)
C6—C3—C4—C5	178.5 (3)	C18—C19—C20—C21	176.1 (4)
C2—C3—C4—C8	−178.2 (3)	C19—C20—C21—C22	175.1 (4)
C6—C3—C4—C8	0.1 (6)	C20—C21—C22—C23	173.7 (3)
C8—C4—C5—C1^i	179.4 (3)	C16—C17—C24—C25	122.9 (6)
C3—C4—C5—C1^i	0.8 (5)	S4—C17—C24—C25	−56.7 (6)
C8—C4—C5—S2	−0.1 (4)	C17—C24—C25—C26	−51.1 (13)
C3—C4—C5—S2	−178.7 (3)	C24—C25—C26—C27	175.6 (9)
C2—C3—C6—C7	0.4 (4)	C25—C26—C27—C28	60.7 (14)
C4—C3—C6—C7	−178.0 (3)	C26—C27—C28—C29	71.9 (10)
C3—C6—C7—C10	179.2 (4)	C25A—C26A—C27A—C28A	160.1 (18)
C3—C6—C7—S1	−0.7 (4)	C26A—C27A—C28A—C29A	−89.7 (17)
C5—C4—C8—C9	−0.2 (4)	C6—C7—S1—C2	0.6 (3)
C3—C4—C8—C9	178.3 (3)	C10—C7—S1—C2	−179.3 (3)
C4—C8—C9—C14	−179.5 (3)	C3—C2—S1—C7	−0.3 (3)
C4—C8—C9—S2	0.4 (4)	C1—C2—S1—C7	178.8 (3)
C6—C7—C10—C11	−169.4 (4)	C8—C9—S2—C5	−0.4 (3)
S1—C7—C10—C11	10.5 (6)	C14—C9—S2—C5	179.6 (3)
C6—C7—C10—S3	10.8 (6)	C4—C5—S2—C9	0.2 (3)
S1—C7—C10—S3	−169.3 (2)	C1^i—C5—S2—C9	−179.2 (3)
C7—C10—C11—C12	179.9 (4)	C11—C10—S3—C13	−0.2 (3)
S3—C10—C11—C12	−0.3 (5)	C7—C10—S3—C13	179.6 (3)
C10—C11—C12—C13	0.9 (6)	C12—C13—S3—C10	0.7 (4)
C11—C12—C13—C18	−178.6 (4)	C18—C13—S3—C10	178.6 (3)
C11—C12—C13—S3	−1.0 (5)	C16—C17—S4—C14	−0.7 (3)
C8—C9—C14—C15	−164.5 (4)	C24—C17—S4—C14	179.0 (3)
S2—C9—C14—C15	15.6 (5)	C15—C14—S4—C17	0.3 (3)
C8—C9—C14—S4	13.1 (5)	C9—C14—S4—C17	−177.7 (3)

Symmetry code: (i) −x, −y+2, −z.