Stacking patterns of thieno[3,2-b]thio­phenes functionalized by sequential palladium-catalyzed Suzuki and Heck cross-coupling reactions

The crystal structures of three 5-alkenyl-2-aryl­thieno[3,2-b]thio­phenes, namely 3,6-di­bromo-5-(4-tert-butyl­styr­yl)-2-(naph­thalen-1-yl)thieno[3,2-b]thio­phene, C₂₈H₂₂Br₂S₂, (I), 3,6-di­bromo-5-(4-methyl­styr­yl)-2-(naphthalen-1-yl)thieno[3,2-b]thio­phene, C₂₅H₁₆Br₂S₂, (II), and 3,6-di­bromo-2-(4-tert-butyl­phen­yl)-5-(4-methyl­styr­yl)thieno[3,2-b]thio­phene, C₂₅H₂₂Br₂S₂, (III), have been determined in order to evaluate the geometry of the mol­ecules. The π-conjugated system containing the thieno[3,2-b]thio­phene skeleton, the ethyl­ene bridge and the phenyl rings is almost planar. The aromatic ring directly attached to the thieno[3,2-b]thio­phene moiety is not coplanar with the thieno[3,2-b]thio­phene moiety itself due to steric hindrance of the bromo substituent. The crystal packings are characterized by π–π stacking [only for (II)] and C—Br...π inter­actions. The long axes of the mol­ecules in (I) are oriented in two directions; for the two other structures the long axis is oriented in one direction only.

S1. Introduction

In the last decade, scientists have been focusing on the development of organic π-conjugated molecules for application in electronic and photonic devices due to their ability to afford high operating speeds, large device densities, low manufacture cost and large-area flexible circuits. Fused thio­phenes are the core structures in many p-type organic semiconductors, low band-gap conjugated oligomers and polymers, photovoltaic devices, dye-sensitizer solar cells and optical materials (Deng et al., 2011; Ito et al., 2013; Kim et al., 2014; Li et al., 2013; Meager et al., 2013). In 2007, Tokiyoshi and co-workers have reported highly crystalline thin films of liquid-crystalline poly[2,5-bis­(3-tetra­decyl­thio­phene-2-yl)thieno[3,2-b]thio­phene] with mobility of up to 0.44 cm² V^-1 s^-1 (Tokiyoshi et al., 2007). Very recently, new D-π-A organic dyes developed by incorporating a thieno[3,2-b]thio­phene moiety as a π-bridge for application in dye-sensitized solar cells (DSSCs) exhibited a remarkable long-term stability and high conversion efficiency (η = 7.00%) comparable to that of the conventional Ru-based dye N719 (η = 7.24%) under the same condition (Lee et al., 2014). Materials containing thieno[3,2-b]thio­phene may increase the electronic transport between neighbouring molecules due to inter­molecular S···S inter­actions. In addition, the introduction of substituents into the core structure of materials may change electronic properties, solubility as well as molecular packing. The high potential application of thieno[3,2-b]thio­phene in electronic materials prompted us to develop an efficient process for the functionalization of thieno[3,2-b]thio­phene via a site-selective palladium(0)-catalyzed Suzuki reaction (Miyaura & Suzuki, 1995; Nicolaou et al., 2005) of tetra­bromo­thieno[3,2-b]thio­phene (Nguyen et al., 2014). In this study, three 5-alkenyl-2-aryl­thieno[3,2-b]thio­phenes, namely 3,6-di­bromo-5-(4-tert-butyl­styryl)-2-(naphthalen-1-yl)thieno[3,2-b]thio­phene, (I), 3,6-di­bromo-5-(4-methyl­styryl)-2-(naphthalen-1-yl)thieno[3,2-b]thio­phene, (II), and 3,6-di­bromo-2-(4-tert-butyl­phenyl)-5-(4-methyl­styryl)thieno[3,2-b]thio­phene, (III), were synthesized by sequential Suzuki and Heck cross-coupling reactions (Baletskaya & Cheprakov, 2000; Nicolaou et al., 2005) and structurally investigated by NMR and single-crystal X-ray diffraction.

S2. Experimental

S2.1. Synthesis and crystallization

A general procedure for the synthesis of 2-aryl-3,5,6-tri­bromo­thieno[3,2-b]thio­phenes as given by Nguyen et al. (2014) was used to synthesize 2,3,6-tri­bromo-5-(naphthalen-1-yl)thieno[3,2-b]thio­phene, (1a), and 2,3,6-tri­bromo-5-(4-tert-butyl­phenyl)­thieno[3,2-b]thio­phene, (1b.

S2.1.1. General procedure for the synthesis of 5-alkenyl-2-aryl-3,6-di­bromo­thieno[3,2-b]thio­phenes (I)–(III)

Di­methyl­formamide (DMF, 4 ml) was deaerated and saturated with argon by exchanging between vacuum and a stream of argon (× 3). Pd(OAc)₂ (0.1 equivalents) and P(Cy)₃ (0.2 equivalents) were dissolved in this argon saturated solvent. The resulting brown–yellow solution was stirred at room temperature for a further 30 min to produce the catalyst. 2-Aryl-3,5,6-tri­bromo­thieno[3,2-b]thio­phene, (1a)/(1b) (1.0 equivalent), Na₂CO₃ (6.0 equivalents) and the alkene (6.0–9.0 equivalents) were added to the solution of the catalyst under a stream of argon. The resulting solution was heated at 363 K with stirring under an argon atmosphere. The progress of the reaction was monitored by thin-layer chromatography (TLC; 100% hexane). When the starting material was completely consumed as indicated by TLC (about 20–24 h), the brownish mixture was allowed to cool to room temperature and filtered to remove the brown precipitate. The filtrate was diluted with ethyl acetate, washed with water (× 3) and dried over anhydrous Na₂SO₄. The solvent was removed under reduced pressure by rotary evaporation and the residue was purified by SiO₂ column chromatography (100% hexane) to give the 5-alkenyl-2-aryl-3,6-di­bromo­thieno[3,2-b]thio­phene.

S2.1.2. Spectroscopic data for 3,6-di­bromo-5-(4-tert-butyl­styryl)-2-(naphthalen-1-yl)thieno[3,2-b]thio­phene, (I)

Starting from (1a) (63 mg, 0.125 mmol) and 4-tert-butyl­styrene (120 mg, 0.75 mmol), (I) was isolated (yield: 20 mg, 27%; m.p. 490–491 K) as an orange solid. ¹H NMR (500 MHz, CDCl₃): δ 7.97 (d, J = 8.0 Hz, 1H, Ar), 7.93 (d, J = 8.0 Hz, 1H, Ar), 7.84 (d, J = 7.5 Hz, 1H, Ar), 7.54 (m, 6H, Ar), 7.41 (d, J = 7.5 Hz, 2H, Ar), 7.32 (d, J = 16.0 Hz, 1H, trans-alkene), 7.07 (d, J = 16.0 Hz, 1H, trans-alkene), 1.35 (s, 9H, tert-butyl). ¹³C NMR (125 MHz, CDCl₃): δ 31.2 (CH₃), 34.8, 103.0, 103.9, 119.6, 125.1, 125.8, 125.9, 126.3, 126.5, 126.8, 128.4, 129.7, 130.0, 130.8, 131.9, 133.5, 133.6, 136.6, 138.4, 139.1, 139.4, 151.8. IR (KBr) (ν, cm^-1): 3064 (w), 2923 (s), 2866 (m), 1635 (m), 1591 (w), 1500 (w), 617 (m), 548 (s).

S2.1.3. Spectroscopic data for 3,6-di­bromo-5-(4-methyl­styryl)-2-(naphthalen-1-yl)thieno[3,2-b]thio­phene, (II)

Starting from (1a) (63 mg, 0.125 mmol) and 4-methyl­styrene (133 mg, 1.125 mmol), (II) was obtained (yield: 15 mg, 22%; m.p. 495–496 K) as a yellow solid. ¹H NMR (500 MHz, CDCl₃): δ 7.96 (d, J = 7.5 Hz, 1H, Ar), 7.93 (d, J = 9.0 Hz, 1H, Ar), 7.85 (d, J = 9.0 Hz, 1H, Ar), 7.53 (m, 4H, Ar), 7.45 (d, J = 8.0 Hz, 2H, Ar), 7.32 (d, J = 16.0 Hz, 1H, trans-alkene), 7.19 (d, J = 7.5 Hz, 2H, Ar), 7.05 (d, J = 16.0 Hz, 1H, trans-alkene), 2.37 (s, 3H, CH₃). ¹³C NMR (125 MHz, CDCl₃): δ 21.3 (CH₃), 102.9, 103.9, 119.3, 125.0; 125.9, 126.3, 126.7, 126.8, 128.4, 129.6, 129.7, 130.0, 130.9, 131.9, 133.5, 133.6, 136.6, 138.4, 138.6, 139.1, 139.3. IR (KBr) (ν, cm^-1): 3050 (w), 2929 (m), 1626 (s), 1546 (m), 1499 (s), 773 (s), 647 (s), 531 (s).

S2.1.4. Spectroscopic data for 3,6-di­bromo-2-(4-tert-butyl­phenyl)-5-(4-methyl­styryl)thieno[3,2-b]thio­phene, (III)

Starting from (1b) (64 mg, 0,125 mmol) and 4-methyl­styrene (133 mg, 1.125 mmol), (III) was obtained as a yellow solid (yield: 13 mg, yield 18%; m.p. 493–494 K). ¹H NMR (500 MHz, CDCl₃): δ 7.63 (d, J = 8.5 Hz, 2H, Ar), 7.46 (d, J = 8.5 Hz, 2H, Ar), 7.40 (d, J = 8.0 Hz, 2H, Ar), 7.24 (d, J = 16.0 Hz, 1H, trans-alkene), 7.16 (d, J = 7.5 Hz, 2H, Ar), 6.97 (d, J = 16.0 Hz, 1H, trans-alkene), 2.36 (s, 3H, CH₃), 1.35 (s, 9H, tert-Butyl). ¹³C NMR (125 MHz, CDCl₃): δ 21.3, 31.2, 34.7, 99.9, 103.0, 119.4, 125.7, 126.6, 128.5, 129.5, 129.9, 130.6, 133.6, 137.7, 137.8, 138.4, 138.8, 140.1, 151.9. IR (KBr) (ν, cm^-1): 3060 (w), 2924 (s), 1619 (w), 1520 (w), 1462 (w), 543 (s).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed in idealized positions and refined in riding mode, with U_iso(H) values assigned as 1.2 times U_eq of the parent atoms (1.5 times for methyl groups) and with C—H distance of 0.95 (aromatic), 0.98 (methyl) and 0.99 Å (methyl­ene).

S3. Results and discussion

All three title compounds, (I)–(III), were characterized by spectroscopic methods (see Experimental). In the ¹H NMR spectra of (I), (II) and (III), it is easy to recognize the signals of the two vicinal olefinic H atoms of the ethyl­ene bridge at about 7.05–7.16 and 7.24–7.23 p.p.m. The splitting of the signals and the typically high coupling constants (16.0 Hz) of these two protons revealed that the cross-coupling happened selectively on the terminal end of the vinyl group, resulting in the formation of trans-alkenes. The regioselectivity of the Suzuki and Heck reactions of 3,5,6-tri­bromo­thieno[3,2-b]thio­phene, (1), however, can only be clarified through single-crystal X-ray diffraction analysis.

The molecular structures of (I)–(III) are shown in Fig. 1. The bond lengths and angles are in good agreement with the average values in the Cambridge Structural Database (CSD, Version 5.35, February 2014; Allen, 2002). The thieno[3,2-b]thio­phene rings are planar, as illustrated by the dihedral angles between the planes of the thio­phene rings, viz. 0.58 (9), 1.29 (12) and 1.74 (10)° for (I), (II) and (III), respectively. In the CSD, this angle ranges between 0.0 and 7.2° and is not related to the substitution pattern [in 3,6-di­bromo-2,5-bis­(thio­phen-2-yl)thieno[3,2-b]thio­phene (refcode WEXBEI; Liu et al., 2013), the central thieno[3,2-b]thio­phene is planar due to the presence of an inversion centre].

In order to enlarge the π-conjugated system of thio­phene, aromatic rings were introduced onto the thieno[3,2-b]thio­phene core structure by sequential Suzuki and Heck cross-coupling reactions. In the resulting compounds, the regioselectivity occured at the C-2 and C-5 atoms at two opposite sides of the thieno[3,2-b]thio­phene ring due to the electron deficiency at these positions.

In all three title compounds, the phenyl fragments attached to the thieno[3,2-b]thio­phene skeleton via an ethyl­ene bridge, and the thieno[3,2-b]thio­phene ring itself make an angle of about 10°. The dihedral angle between these mean planes is 14.05 (7)° in (I), 10.04 (10)° in (II) and 10.09 (8)° in (III), illustrating that π-conjugation is still favourable due to the ethyl­ene bridges. However, in the case of the tert-butyl group in (I), the dihedral angle is slightly larger. The CSD only lists three entries containing a thieno[3,2-b]thio­phene skeleton and a phenyl ring linked to each other via an ethyl­ene bridge [2,2'-(bi­phenyl-4,4'-diyldiethene-2,1-diyl)bis­(thieno[3,2-b]thio­phene) (refcode ARIFEN; Li et al., 2011), 2,6-bis­(2-phenyl­vinyl)­bis­thieno[3,2-b:2',3'-d]thio­phene (refcode GURQAM; Liu et al., 2010) and 2,6-bis­(2-phenyl­vinyl)­thieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thio­phene (refcode GURQEQ; Liu et al., 2010)]. In each case, the angle between the mean planes through both planes is less than 10°. In GURQAM and GURQEQ, the thieno[3,2-b]thio­phene skeleton is further extended to bis­thieno[3,2-b:2',3'-d]thio­phene and thieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thio­phene, respectively. Also in ARIFEN, no substituents are present on the conjugated system. As expected, the stereochemistry around the ethyl­ene bridge is always E. The aromatic rings directly connected to the thieno[3,2-b]thio­phene moiety by the Suzuki reaction, show no coplanarity with the rest of the molecule. In (I) and (II), the naphthalene rings are rotated out of the plane of the thieno[3,2-b]thio­phene ring by dihedral angles of 65.77 (5) and 52.68 (7)°, respectively. This rotation reduces the repulsion between atoms Br10···H31 and S6···H24 in (I) and between atoms Br10···H29 and S6···H21 in (II). The dihedral angle between the plane of the thieno[3,2-b]thio­phene system and that of the smaller phenyl ring in (III) is reduced to 41.49 (8)°, which correlates well with the related compounds (Liu et al., 2013). However, the tert-butyl substituent makes the tert-butyl­phenyl group slightly bent. Thus, the angles between the C20—C7 and C26—C23 bonds and the benzene ring are 6.30 (14) and 6.48 (13)°, respectively.

The packings of (I) and (III) show no π–π stacking, although they consist of a number of aromatic moieties. However, compound (II) displays π–π stacking inter­actions between naphthalene rings [Cg1···Cg2ⁱ = 3.6951 (16) Å; Cg1 and Cg2 are the centroids of the C20–C25 and C24–C29 rings, respectively; symmetry code: (i) x+1, y, z; Fig. 2]. This could be due to the absence of the tert-butyl group, allowing a closer molecule arrangement.

All three title structures show to a certain extent C—Br···π inter­actions. This inter­action is most favourable in (I) [C8—Br10···Cg3ⁱⁱ = 3.5695 (10) Å, C3—Br9···Cg4ⁱⁱⁱ = 3.5412 (10) Å and C3—Br9···Cg3ⁱ = 3.8651 (11) Å; Cg3 and Cg4 are the centroids of the C13–C18 and S1/C2–C5 rings, respectively; symmetry codes: (ii) -x, y+1/2, -z+3/2; (iii) -x, -y+2, -z+1; Fig. 3]. The C—Br···π inter­actions are less prominent present in the two other structures [C3—Br9···Cg5^iv = 3.9496 (11) Å for (II) and C3—Br9···Cg6^v = 3.8542 (10) Å for (III); Cg5 and Cg6 are the centroids of the S1/C2—C5 and C4–C5/S6/C7–C8 rings, respectively; symmetry codes: (iv) x-1, y, z; (v) -x+1, -y+1, -z+1; Figs. 4 and 5]. In the case of (I), the long axis of the molecules is oriented in two directions, viz. [210] and [2 10]. For the two other structures, the long axis is oriented in only one direction, viz. [031] for (II) and [110] for (III). Possible inter­molecular S···S inter­actions, which may influence the electronic transport between neighbouring molecules, are only observed for (I). However, this inter­action is weak [S6···S6^vi = 3.819 Å; symmetry code: (vi) -x+1, -y+2, -z+1].

Related literature

For related literature, see: Allen (2002); Baletskaya & Cheprakov (2000); Deng et al. (2011); Ito et al. (2013); Kim et al. (2014); Lee et al. (2014); Li et al. (2011, 2013); Liu et al. (2010, 2013); Meager et al. (2013); Miyaura & Suzuki (1995); Nguyen et al. (2014); Nicolaou et al. (2005); Tokiyoshi et al. (2007).

Computing details

Data collection: CrysAlis PRO, Version 1.171.36.28 (Agilent, 2012) for (I); (CrysAlis PRO; Agilent, 2012) for (II), (III). Cell refinement: CrysAlis PRO, Version 1.171.36.28 (Agilent, 2012) for (I); (CrysAlis PRO; Agilent, 2012) for (II), (III). Data reduction: CrysAlis PRO, Version 1.171.36.28 (Agilent, 2012) for (I); (CrysAlis PRO; Agilent, 2012) for (II), (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); XS (Sheldrick, 2008) for (II), (III). For all compounds, program(s) used to refine structure: XL (Sheldrick, 2008); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Figures

	Fig. 1. Views of the asymmetric units in (a) (I), (b) (II) and (c) (III), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. π–π stacking (red dotted line) in (II) [Cg1 and Cg2 are the centroids of the C20–C25 and C25–C29 rings, respectively; symmetry code: (i) x+1, y, z.]
	Fig. 3. C—Br···π interactions in (I) [Cg3 and Cg4 are the centroids of the C13–C18 and S1/C2–C5 rings, respectively; symmetry codes: (i) x+1, y, z; (ii) -x, y+1/2, -z+3/2; (iii) -x, -y+2, -z+1.]
	Fig. 4. C—Br···π interactions in (II) [Cg5 is the centroid of the S1/C2–C5 ring; symmetry code: (iv) x-1, y, z.]
	Fig. 5. C—Br···π interactions in (III) [Cg6 is the centroid of the C4–C5/S6/C7–C8 ring; symmetry code: (v) -x+1, -y+1, -z+1.]

(I) 3,6-Dibromo-5-(4-tert-butylstyryl)2-(naphthalen-1-yl)thieno[3,2-b]thiophene

Crystal data

C28H22Br2S2	F(000) = 1168
Mr = 582.40	Dx = 1.594 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.3316 (3) Å	Cell parameters from 12479 reflections
b = 16.1749 (6) Å	θ = 3.1–29.0°
c = 18.1333 (6) Å	µ = 3.53 mm^−1
β = 96.677 (3)°	T = 100 K
V = 2427.13 (15) Å^3	Prism, orange
Z = 4	0.3 × 0.15 × 0.15 mm

Data collection

Agilent SuperNova diffractometer (Single source at offset, Eos detector)	4962 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4491 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 15.9631 pixels mm^-1	θmax = 26.4°, θmin = 2.8°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −20→20
Tmin = 0.681, Tmax = 1.000	l = −22→22
25300 measured reflections

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.051	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.019P)^2 + 1.8507P] where P = (Fo^2 + 2Fc^2)/3
4962 reflections	(Δ/σ)max = 0.002
292 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.27 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
S1	0.00853 (5)	0.96982 (3)	0.68447 (2)	0.01444 (10)
C2	0.0013 (2)	0.91490 (12)	0.60029 (10)	0.0155 (4)
C3	0.1292 (2)	0.93567 (11)	0.56283 (10)	0.0147 (4)
C4	0.2305 (2)	0.99653 (11)	0.59933 (10)	0.0137 (4)
C5	0.1812 (2)	1.02135 (11)	0.66578 (10)	0.0136 (4)
S6	0.40170 (5)	1.04792 (3)	0.58019 (2)	0.01574 (10)
C7	0.4082 (2)	1.10340 (11)	0.66312 (10)	0.0147 (4)
C8	0.2845 (2)	1.08156 (11)	0.70254 (10)	0.0140 (4)
Br9	0.16772 (2)	0.890916 (11)	0.470787 (10)	0.01708 (5)
Br10	0.26100 (2)	1.123191 (12)	0.797833 (10)	0.01786 (6)
C11	−0.1291 (2)	0.85885 (12)	0.57696 (10)	0.0170 (4)
H11	−0.1181	0.8254	0.5348	0.020*
C12	−0.2641 (2)	0.84965 (12)	0.60935 (10)	0.0171 (4)
H12	−0.2750	0.8836	0.6512	0.021*
C13	−0.3968 (2)	0.79259 (12)	0.58677 (10)	0.0167 (4)
C14	−0.5332 (2)	0.79350 (12)	0.62447 (10)	0.0174 (4)
H14	−0.5410	0.8334	0.6623	0.021*
C15	−0.6577 (2)	0.73751 (12)	0.60799 (10)	0.0186 (4)
H15	−0.7488	0.7397	0.6350	0.022*
C16	−0.6528 (2)	0.67819 (12)	0.55286 (10)	0.0169 (4)
C17	−0.5183 (2)	0.67923 (14)	0.51340 (11)	0.0247 (5)
H17	−0.5128	0.6407	0.4742	0.030*
C18	−0.3934 (2)	0.73456 (13)	0.52972 (11)	0.0239 (4)
H18	−0.3038	0.7333	0.5018	0.029*
C19	−0.7904 (2)	0.61567 (12)	0.53462 (10)	0.0188 (4)
C20	−0.9133 (3)	0.65201 (15)	0.47382 (13)	0.0353 (6)
H20A	−0.9998	0.6118	0.4605	0.053*
H20B	−0.8593	0.6647	0.4299	0.053*
H20C	−0.9594	0.7028	0.4921	0.053*
C21	−0.8750 (3)	0.59631 (16)	0.60343 (12)	0.0348 (6)
H21A	−0.9546	0.5523	0.5916	0.052*
H21B	−0.9297	0.6461	0.6186	0.052*
H21C	−0.7946	0.5783	0.6440	0.052*
C22	−0.7260 (3)	0.53419 (13)	0.50670 (13)	0.0306 (5)
H22A	−0.6376	0.5140	0.5425	0.046*
H22B	−0.6861	0.5433	0.4586	0.046*
H22C	−0.8131	0.4932	0.5011	0.046*
C23	0.5400 (2)	1.16410 (12)	0.68043 (10)	0.0150 (4)
C24	0.6970 (2)	1.13650 (12)	0.69203 (10)	0.0178 (4)
H24	0.7178	1.0788	0.6905	0.021*
C25	0.8273 (2)	1.19146 (13)	0.70602 (10)	0.0208 (4)
H25	0.9347	1.1709	0.7142	0.025*
C26	0.7993 (2)	1.27443 (13)	0.70781 (10)	0.0210 (4)
H26	0.8879	1.3114	0.7173	0.025*
C27	0.6397 (2)	1.30641 (12)	0.69573 (10)	0.0189 (4)
C28	0.6092 (3)	1.39219 (13)	0.69696 (11)	0.0238 (4)
H28	0.6974	1.4296	0.7051	0.029*
C29	0.4560 (3)	1.42220 (13)	0.68672 (11)	0.0273 (5)
H29	0.4378	1.4801	0.6887	0.033*
C30	0.3238 (3)	1.36753 (13)	0.67316 (11)	0.0248 (4)
H30	0.2169	1.3889	0.6658	0.030*
C31	0.3483 (2)	1.28412 (12)	0.67051 (10)	0.0194 (4)
H31	0.2583	1.2481	0.6607	0.023*
C32	0.5070 (2)	1.25076 (12)	0.68225 (10)	0.0160 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0126 (2)	0.0167 (2)	0.0141 (2)	−0.00241 (17)	0.00161 (17)	−0.00025 (17)
C2	0.0162 (9)	0.0146 (9)	0.0147 (9)	−0.0008 (7)	−0.0022 (7)	0.0011 (7)
C3	0.0160 (9)	0.0143 (9)	0.0135 (9)	0.0010 (7)	−0.0002 (7)	−0.0002 (7)
C4	0.0129 (9)	0.0130 (9)	0.0151 (9)	−0.0007 (7)	0.0006 (7)	0.0010 (7)
C5	0.0121 (9)	0.0142 (9)	0.0144 (9)	−0.0004 (7)	0.0007 (7)	0.0023 (7)
S6	0.0153 (2)	0.0176 (2)	0.0148 (2)	−0.00484 (18)	0.00368 (17)	−0.00338 (17)
C7	0.0150 (9)	0.0137 (9)	0.0148 (9)	0.0001 (7)	−0.0007 (7)	−0.0010 (7)
C8	0.0142 (9)	0.0147 (9)	0.0127 (8)	0.0023 (7)	0.0004 (7)	−0.0012 (7)
Br9	0.01942 (10)	0.01777 (10)	0.01416 (9)	−0.00291 (7)	0.00246 (7)	−0.00312 (7)
Br10	0.01814 (10)	0.02115 (10)	0.01455 (10)	−0.00166 (7)	0.00306 (7)	−0.00452 (7)
C11	0.0170 (9)	0.0174 (10)	0.0157 (9)	−0.0030 (8)	−0.0012 (7)	−0.0006 (7)
C12	0.0196 (10)	0.0175 (10)	0.0136 (9)	−0.0037 (8)	−0.0011 (7)	−0.0004 (7)
C13	0.0153 (9)	0.0189 (10)	0.0153 (9)	−0.0028 (8)	−0.0014 (7)	0.0032 (7)
C14	0.0186 (10)	0.0182 (10)	0.0154 (9)	−0.0008 (8)	0.0025 (7)	−0.0009 (7)
C15	0.0158 (9)	0.0215 (10)	0.0190 (10)	−0.0024 (8)	0.0043 (7)	0.0019 (8)
C16	0.0155 (9)	0.0190 (10)	0.0155 (9)	−0.0044 (8)	−0.0014 (7)	0.0031 (7)
C17	0.0256 (11)	0.0303 (12)	0.0191 (10)	−0.0100 (9)	0.0060 (8)	−0.0090 (9)
C18	0.0197 (10)	0.0328 (12)	0.0209 (10)	−0.0098 (9)	0.0092 (8)	−0.0049 (9)
C19	0.0175 (9)	0.0211 (10)	0.0176 (9)	−0.0082 (8)	0.0017 (8)	0.0011 (8)
C20	0.0265 (12)	0.0323 (13)	0.0430 (14)	−0.0126 (10)	−0.0130 (10)	0.0108 (10)
C21	0.0349 (13)	0.0426 (14)	0.0286 (12)	−0.0226 (11)	0.0116 (10)	−0.0054 (10)
C22	0.0262 (12)	0.0225 (12)	0.0441 (13)	−0.0104 (9)	0.0078 (10)	−0.0037 (10)
C23	0.0169 (9)	0.0177 (10)	0.0106 (8)	−0.0034 (7)	0.0022 (7)	−0.0020 (7)
C24	0.0183 (10)	0.0203 (10)	0.0149 (9)	0.0003 (8)	0.0025 (7)	−0.0021 (7)
C25	0.0143 (9)	0.0287 (11)	0.0191 (9)	−0.0010 (8)	0.0009 (8)	−0.0030 (8)
C26	0.0197 (10)	0.0270 (11)	0.0160 (9)	−0.0100 (8)	−0.0001 (8)	−0.0023 (8)
C27	0.0244 (10)	0.0201 (10)	0.0119 (9)	−0.0047 (8)	0.0005 (8)	−0.0017 (7)
C28	0.0314 (12)	0.0198 (10)	0.0186 (10)	−0.0078 (9)	−0.0037 (8)	0.0005 (8)
C29	0.0415 (13)	0.0159 (10)	0.0225 (11)	−0.0004 (9)	−0.0048 (9)	0.0004 (8)
C30	0.0261 (11)	0.0237 (11)	0.0231 (10)	0.0059 (9)	−0.0028 (8)	0.0012 (8)
C31	0.0214 (10)	0.0196 (10)	0.0165 (9)	−0.0004 (8)	−0.0003 (8)	0.0000 (7)
C32	0.0200 (9)	0.0172 (10)	0.0105 (8)	−0.0019 (8)	0.0006 (7)	−0.0005 (7)

Geometric parameters (Å, º)

S1—C2	1.7612 (18)	C19—C21	1.535 (3)
S1—C5	1.7297 (18)	C19—C22	1.531 (3)
C2—C3	1.370 (3)	C20—H20A	0.9800
C2—C11	1.440 (3)	C20—H20B	0.9800
C3—C4	1.411 (2)	C20—H20C	0.9800
C3—Br9	1.8809 (18)	C21—H21A	0.9800
C4—C5	1.378 (3)	C21—H21B	0.9800
C4—S6	1.7205 (18)	C21—H21C	0.9800
C5—C8	1.414 (3)	C22—H22A	0.9800
S6—C7	1.7467 (18)	C22—H22B	0.9800
C7—C8	1.367 (3)	C22—H22C	0.9800
C7—C23	1.479 (3)	C23—C24	1.375 (3)
C8—Br10	1.8858 (17)	C23—C32	1.429 (3)
C11—H11	0.9500	C24—H24	0.9500
C11—C12	1.337 (3)	C24—C25	1.403 (3)
C12—H12	0.9500	C25—H25	0.9500
C12—C13	1.462 (3)	C25—C26	1.363 (3)
C13—C14	1.393 (3)	C26—H26	0.9500
C13—C18	1.400 (3)	C26—C27	1.420 (3)
C14—H14	0.9500	C27—C28	1.411 (3)
C14—C15	1.383 (3)	C27—C32	1.424 (3)
C15—H15	0.9500	C28—H28	0.9500
C15—C16	1.390 (3)	C28—C29	1.358 (3)
C16—C17	1.398 (3)	C29—H29	0.9500
C16—C19	1.536 (3)	C29—C30	1.412 (3)
C17—H17	0.9500	C30—H30	0.9500
C17—C18	1.378 (3)	C30—C31	1.366 (3)
C18—H18	0.9500	C31—H31	0.9500
C19—C20	1.532 (3)	C31—C32	1.422 (3)
C5—S1—C2	91.06 (9)	C22—C19—C21	107.75 (17)
C3—C2—S1	110.85 (14)	C19—C20—H20A	109.5
C3—C2—C11	127.75 (17)	C19—C20—H20B	109.5
C11—C2—S1	121.37 (14)	C19—C20—H20C	109.5
C2—C3—C4	113.34 (16)	H20A—C20—H20B	109.5
C2—C3—Br9	124.64 (14)	H20A—C20—H20C	109.5
C4—C3—Br9	122.01 (13)	H20B—C20—H20C	109.5
C3—C4—S6	135.04 (14)	C19—C21—H21A	109.5
C5—C4—C3	112.97 (16)	C19—C21—H21B	109.5
C5—C4—S6	111.99 (14)	C19—C21—H21C	109.5
C4—C5—S1	111.76 (14)	H21A—C21—H21B	109.5
C4—C5—C8	112.68 (16)	H21A—C21—H21C	109.5
C8—C5—S1	135.55 (14)	H21B—C21—H21C	109.5
C4—S6—C7	91.04 (9)	C19—C22—H22A	109.5
C8—C7—S6	111.56 (14)	C19—C22—H22B	109.5
C8—C7—C23	130.29 (17)	C19—C22—H22C	109.5
C23—C7—S6	118.15 (13)	H22A—C22—H22B	109.5
C5—C8—Br10	123.73 (13)	H22A—C22—H22C	109.5
C7—C8—C5	112.71 (16)	H22B—C22—H22C	109.5
C7—C8—Br10	123.48 (14)	C24—C23—C7	119.10 (17)
C2—C11—H11	117.1	C24—C23—C32	119.78 (17)
C12—C11—C2	125.86 (18)	C32—C23—C7	121.08 (17)
C12—C11—H11	117.1	C23—C24—H24	119.2
C11—C12—H12	116.7	C23—C24—C25	121.61 (19)
C11—C12—C13	126.51 (18)	C25—C24—H24	119.2
C13—C12—H12	116.7	C24—C25—H25	120.1
C14—C13—C12	119.31 (17)	C26—C25—C24	119.80 (19)
C14—C13—C18	117.22 (17)	C26—C25—H25	120.1
C18—C13—C12	123.45 (17)	C25—C26—H26	119.5
C13—C14—H14	119.3	C25—C26—C27	120.99 (18)
C15—C14—C13	121.42 (18)	C27—C26—H26	119.5
C15—C14—H14	119.3	C26—C27—C32	119.37 (18)
C14—C15—H15	119.2	C28—C27—C26	121.53 (18)
C14—C15—C16	121.54 (17)	C28—C27—C32	119.10 (19)
C16—C15—H15	119.2	C27—C28—H28	119.4
C15—C16—C17	116.90 (17)	C29—C28—C27	121.17 (19)
C15—C16—C19	121.71 (17)	C29—C28—H28	119.4
C17—C16—C19	121.37 (17)	C28—C29—H29	119.9
C16—C17—H17	119.1	C28—C29—C30	120.1 (2)
C18—C17—C16	121.86 (18)	C30—C29—H29	119.9
C18—C17—H17	119.1	C29—C30—H30	119.7
C13—C18—H18	119.5	C31—C30—C29	120.5 (2)
C17—C18—C13	120.99 (18)	C31—C30—H30	119.7
C17—C18—H18	119.5	C30—C31—H31	119.7
C20—C19—C16	108.79 (16)	C30—C31—C32	120.65 (19)
C20—C19—C21	109.38 (18)	C32—C31—H31	119.7
C21—C19—C16	111.17 (16)	C27—C32—C23	118.45 (17)
C22—C19—C16	110.88 (16)	C31—C32—C23	123.13 (17)
C22—C19—C20	108.83 (18)	C31—C32—C27	118.42 (18)
S1—C2—C3—C4	−1.6 (2)	C11—C12—C13—C18	4.8 (3)
S1—C2—C3—Br9	179.68 (10)	C12—C13—C14—C15	−176.21 (18)
S1—C2—C11—C12	8.7 (3)	C12—C13—C18—C17	176.4 (2)
S1—C5—C8—C7	−179.54 (16)	C13—C14—C15—C16	−0.4 (3)
S1—C5—C8—Br10	3.5 (3)	C14—C13—C18—C17	−1.9 (3)
C2—S1—C5—C4	−0.83 (14)	C14—C15—C16—C17	−1.8 (3)
C2—S1—C5—C8	−179.7 (2)	C14—C15—C16—C19	179.73 (18)
C2—C3—C4—C5	1.0 (2)	C15—C16—C17—C18	2.1 (3)
C2—C3—C4—S6	−178.48 (16)	C15—C16—C19—C20	90.7 (2)
C2—C11—C12—C13	−179.42 (18)	C15—C16—C19—C21	−29.8 (3)
C3—C2—C11—C12	−169.04 (19)	C15—C16—C19—C22	−149.62 (19)
C3—C4—C5—S1	0.1 (2)	C16—C17—C18—C13	−0.2 (3)
C3—C4—C5—C8	179.22 (16)	C17—C16—C19—C20	−87.7 (2)
C3—C4—S6—C7	179.9 (2)	C17—C16—C19—C21	151.8 (2)
C4—C5—C8—C7	1.6 (2)	C17—C16—C19—C22	31.9 (3)
C4—C5—C8—Br10	−175.38 (13)	C18—C13—C14—C15	2.2 (3)
C4—S6—C7—C8	0.55 (15)	C19—C16—C17—C18	−179.42 (19)
C4—S6—C7—C23	−179.67 (15)	C23—C7—C8—C5	178.96 (18)
C5—S1—C2—C3	1.41 (15)	C23—C7—C8—Br10	−4.1 (3)
C5—S1—C2—C11	−176.66 (16)	C23—C24—C25—C26	−0.4 (3)
C5—C4—S6—C7	0.35 (15)	C24—C23—C32—C27	0.4 (3)
S6—C4—C5—S1	179.71 (9)	C24—C23—C32—C31	179.74 (17)
S6—C4—C5—C8	−1.1 (2)	C24—C25—C26—C27	0.0 (3)
S6—C7—C8—C5	−1.3 (2)	C25—C26—C27—C28	−179.58 (18)
S6—C7—C8—Br10	175.67 (10)	C25—C26—C27—C32	0.6 (3)
S6—C7—C23—C24	−64.6 (2)	C26—C27—C28—C29	−178.76 (18)
S6—C7—C23—C32	112.86 (17)	C26—C27—C32—C23	−0.8 (3)
C7—C23—C24—C25	177.69 (17)	C26—C27—C32—C31	179.82 (17)
C7—C23—C32—C27	−177.02 (16)	C27—C28—C29—C30	−1.2 (3)
C7—C23—C32—C31	2.3 (3)	C28—C27—C32—C23	179.38 (17)
C8—C7—C23—C24	115.1 (2)	C28—C27—C32—C31	0.0 (3)
C8—C7—C23—C32	−67.4 (3)	C28—C29—C30—C31	0.3 (3)
Br9—C3—C4—C5	179.76 (13)	C29—C30—C31—C32	0.8 (3)
Br9—C3—C4—S6	0.2 (3)	C30—C31—C32—C23	179.75 (18)
C11—C2—C3—C4	176.27 (18)	C30—C31—C32—C27	−0.9 (3)
C11—C2—C3—Br9	−2.4 (3)	C32—C23—C24—C25	0.2 (3)
C11—C12—C13—C14	−176.89 (19)	C32—C27—C28—C29	1.0 (3)

(II) 3,6-Dibromo-5-(4-methylstyryl)-2-(naphthalen-1-yl)thieno[3,2-b]thiophene

Crystal data

C25H16Br2S2	Z = 2
Mr = 540.32	F(000) = 536
Triclinic, P1	Dx = 1.742 Mg m^−3
a = 4.1522 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.2861 (14) Å	Cell parameters from 11208 reflections
c = 19.6117 (18) Å	θ = 3.2–29.0°
α = 106.464 (9)°	µ = 4.15 mm^−1
β = 94.945 (7)°	T = 100 K
γ = 93.016 (7)°	Prism, yellow
V = 1030.32 (16) Å^3	0.4 × 0.15 × 0.05 mm

Data collection

Agilent SuperNova diffractometer (Single source at offset, Eos detector)	4207 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3705 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.043
Detector resolution: 15.9631 pixels mm^-1	θmax = 26.4°, θmin = 3.1°
ω scans	h = −5→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −16→16
Tmin = 0.455, Tmax = 1.000	l = −24→24
20862 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 0.857P] where P = (Fo^2 + 2Fc^2)/3
4207 reflections	(Δ/σ)max = 0.001
263 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.49 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
Br9	−0.35388 (6)	0.232660 (19)	0.371943 (13)	0.01906 (9)
Br10	0.39181 (6)	0.545455 (19)	0.192448 (12)	0.01776 (8)
C2	−0.1827 (6)	0.2195 (2)	0.23021 (13)	0.0158 (5)
C3	−0.1770 (6)	0.27901 (19)	0.30016 (13)	0.0154 (5)
C4	−0.0242 (6)	0.38101 (19)	0.31388 (13)	0.0158 (5)
C5	0.0795 (6)	0.4009 (2)	0.25420 (13)	0.0156 (5)
C7	0.2307 (6)	0.56396 (19)	0.33719 (13)	0.0153 (5)
C8	0.2226 (6)	0.5042 (2)	0.26721 (13)	0.0156 (5)
C11	−0.3148 (6)	0.1121 (2)	0.19773 (14)	0.0168 (5)
H11	−0.4334	0.0798	0.2263	0.020*
C12	−0.2850 (6)	0.0541 (2)	0.13097 (14)	0.0186 (5)
H12	−0.1671	0.0870	0.1026	0.022*
C13	−0.4148 (6)	−0.05453 (19)	0.09730 (13)	0.0156 (5)
C14	−0.5996 (6)	−0.1120 (2)	0.13151 (13)	0.0178 (5)
H14	−0.6502	−0.0792	0.1786	0.021*
C15	−0.7111 (7)	−0.2157 (2)	0.09825 (14)	0.0195 (6)
H15	−0.8339	−0.2533	0.1232	0.023*
C16	−0.6465 (6)	−0.26626 (19)	0.02888 (13)	0.0175 (5)
C17	−0.4658 (7)	−0.2095 (2)	−0.00600 (14)	0.0194 (6)
H17	−0.4201	−0.2421	−0.0535	0.023*
C18	−0.3510 (6)	−0.1059 (2)	0.02740 (13)	0.0184 (5)
H18	−0.2264	−0.0688	0.0025	0.022*
C19	−0.7751 (7)	−0.3789 (2)	−0.00734 (15)	0.0244 (6)
H19A	−0.7312	−0.4216	0.0253	0.037*
H19B	−0.6680	−0.4065	−0.0507	0.037*
H19C	−1.0095	−0.3819	−0.0201	0.037*
C20	0.3603 (6)	0.67262 (19)	0.37607 (13)	0.0153 (5)
C21	0.5603 (6)	0.6898 (2)	0.43878 (13)	0.0166 (5)
H21	0.6050	0.6320	0.4566	0.020*
C22	0.6998 (7)	0.7911 (2)	0.47697 (13)	0.0197 (6)
H22	0.8368	0.8010	0.5201	0.024*
C23	0.6391 (7)	0.8751 (2)	0.45228 (13)	0.0191 (6)
H23	0.7442	0.9425	0.4768	0.023*
C24	0.4210 (6)	0.8628 (2)	0.39039 (13)	0.0167 (5)
C25	0.2769 (6)	0.76085 (19)	0.35194 (13)	0.0146 (5)
C26	0.3404 (7)	0.9507 (2)	0.36704 (14)	0.0206 (6)
H26	0.4426	1.0184	0.3919	0.025*
C27	0.1192 (7)	0.9397 (2)	0.30972 (14)	0.0226 (6)
H27	0.0665	0.9995	0.2948	0.027*
C28	−0.0321 (7)	0.8394 (2)	0.27242 (14)	0.0213 (6)
H28	−0.1888	0.8319	0.2327	0.026*
C29	0.0448 (6)	0.7527 (2)	0.29288 (13)	0.0168 (5)
H29	−0.0594	0.6857	0.2670	0.020*
S1	−0.00132 (16)	0.29277 (5)	0.17990 (3)	0.01613 (14)
S6	0.05858 (16)	0.48915 (5)	0.38773 (3)	0.01611 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br9	0.02471 (17)	0.01620 (14)	0.01796 (14)	0.00009 (11)	0.00276 (11)	0.00779 (10)
Br10	0.02196 (16)	0.01626 (14)	0.01408 (13)	−0.00284 (10)	0.00263 (10)	0.00339 (10)
C2	0.0156 (14)	0.0148 (12)	0.0180 (12)	0.0015 (10)	0.0012 (10)	0.0063 (10)
C3	0.0191 (14)	0.0136 (12)	0.0153 (12)	0.0022 (10)	0.0004 (10)	0.0072 (10)
C4	0.0173 (14)	0.0137 (12)	0.0160 (12)	0.0034 (10)	0.0007 (10)	0.0036 (10)
C5	0.0153 (13)	0.0151 (12)	0.0149 (12)	0.0024 (10)	−0.0002 (10)	0.0024 (10)
C7	0.0179 (14)	0.0131 (12)	0.0157 (12)	0.0014 (10)	0.0024 (10)	0.0055 (10)
C8	0.0173 (14)	0.0155 (12)	0.0145 (12)	0.0008 (10)	0.0000 (10)	0.0057 (10)
C11	0.0152 (13)	0.0156 (13)	0.0207 (13)	0.0004 (10)	−0.0012 (10)	0.0080 (10)
C12	0.0181 (14)	0.0175 (13)	0.0207 (13)	−0.0003 (11)	0.0004 (11)	0.0074 (11)
C13	0.0149 (13)	0.0137 (12)	0.0172 (12)	0.0019 (10)	−0.0019 (10)	0.0038 (10)
C14	0.0219 (15)	0.0158 (13)	0.0151 (12)	0.0024 (11)	0.0008 (10)	0.0035 (10)
C15	0.0233 (15)	0.0157 (13)	0.0207 (13)	−0.0015 (11)	0.0004 (11)	0.0085 (10)
C16	0.0179 (14)	0.0136 (12)	0.0188 (13)	0.0026 (10)	−0.0038 (10)	0.0026 (10)
C17	0.0231 (15)	0.0168 (13)	0.0169 (12)	0.0031 (11)	0.0014 (11)	0.0027 (10)
C18	0.0212 (15)	0.0178 (13)	0.0167 (12)	−0.0009 (11)	0.0026 (10)	0.0060 (10)
C19	0.0283 (16)	0.0137 (13)	0.0272 (14)	−0.0012 (12)	−0.0017 (12)	0.0016 (11)
C20	0.0171 (14)	0.0135 (12)	0.0138 (12)	0.0009 (10)	0.0054 (10)	0.0006 (10)
C21	0.0196 (14)	0.0164 (13)	0.0146 (12)	0.0046 (11)	0.0036 (10)	0.0049 (10)
C22	0.0197 (15)	0.0226 (14)	0.0133 (12)	0.0017 (11)	0.0008 (10)	−0.0001 (10)
C23	0.0191 (14)	0.0167 (13)	0.0174 (12)	−0.0044 (11)	0.0027 (10)	−0.0007 (10)
C24	0.0176 (14)	0.0154 (13)	0.0165 (12)	0.0015 (10)	0.0073 (10)	0.0018 (10)
C25	0.0163 (13)	0.0139 (12)	0.0137 (11)	0.0011 (10)	0.0045 (10)	0.0032 (10)
C26	0.0264 (16)	0.0147 (13)	0.0200 (13)	−0.0010 (11)	0.0113 (11)	0.0017 (10)
C27	0.0306 (17)	0.0181 (14)	0.0247 (14)	0.0087 (12)	0.0123 (12)	0.0114 (11)
C28	0.0217 (15)	0.0247 (14)	0.0199 (13)	0.0058 (12)	0.0058 (11)	0.0087 (11)
C29	0.0172 (14)	0.0170 (13)	0.0152 (12)	0.0002 (10)	0.0027 (10)	0.0032 (10)
S1	0.0215 (4)	0.0124 (3)	0.0129 (3)	−0.0017 (2)	0.0003 (2)	0.0019 (2)
S6	0.0227 (4)	0.0121 (3)	0.0129 (3)	0.0009 (3)	0.0025 (2)	0.0026 (2)

Geometric parameters (Å, º)

Br9—C3	1.877 (2)	C17—H17	0.9500
Br10—C8	1.880 (2)	C17—C18	1.385 (4)
C2—C3	1.373 (3)	C18—H18	0.9500
C2—C11	1.445 (4)	C19—H19A	0.9800
C2—S1	1.756 (3)	C19—H19B	0.9800
C3—C4	1.409 (4)	C19—H19C	0.9800
C4—C5	1.369 (4)	C20—C21	1.378 (4)
C4—S6	1.721 (2)	C20—C25	1.431 (3)
C5—C8	1.412 (4)	C21—H21	0.9500
C5—S1	1.726 (2)	C21—C22	1.407 (4)
C7—C8	1.373 (3)	C22—H22	0.9500
C7—C20	1.476 (3)	C22—C23	1.363 (4)
C7—S6	1.757 (3)	C23—H23	0.9500
C11—H11	0.9500	C23—C24	1.415 (4)
C11—C12	1.338 (4)	C24—C25	1.421 (3)
C12—H12	0.9500	C24—C26	1.415 (4)
C12—C13	1.458 (4)	C25—C29	1.417 (4)
C13—C14	1.393 (4)	C26—H26	0.9500
C13—C18	1.402 (3)	C26—C27	1.358 (4)
C14—H14	0.9500	C27—H27	0.9500
C14—C15	1.382 (4)	C27—C28	1.409 (4)
C15—H15	0.9500	C28—H28	0.9500
C15—C16	1.392 (4)	C28—C29	1.367 (4)
C16—C17	1.386 (4)	C29—H29	0.9500
C16—C19	1.510 (3)
C3—C2—C11	128.2 (2)	C17—C18—C13	121.3 (2)
C3—C2—S1	110.50 (19)	C17—C18—H18	119.3
C11—C2—S1	121.31 (19)	C16—C19—H19A	109.5
C2—C3—Br9	124.7 (2)	C16—C19—H19B	109.5
C2—C3—C4	113.3 (2)	C16—C19—H19C	109.5
C4—C3—Br9	122.04 (18)	H19A—C19—H19B	109.5
C3—C4—S6	135.5 (2)	H19A—C19—H19C	109.5
C5—C4—C3	113.2 (2)	H19B—C19—H19C	109.5
C5—C4—S6	111.3 (2)	C21—C20—C7	118.8 (2)
C4—C5—C8	113.4 (2)	C21—C20—C25	119.0 (2)
C4—C5—S1	111.6 (2)	C25—C20—C7	122.1 (2)
C8—C5—S1	135.0 (2)	C20—C21—H21	119.3
C8—C7—C20	133.1 (2)	C20—C21—C22	121.4 (2)
C8—C7—S6	109.98 (19)	C22—C21—H21	119.3
C20—C7—S6	116.85 (18)	C21—C22—H22	119.9
C5—C8—Br10	119.77 (18)	C23—C22—C21	120.2 (2)
C7—C8—Br10	126.8 (2)	C23—C22—H22	119.9
C7—C8—C5	113.4 (2)	C22—C23—H23	119.7
C2—C11—H11	117.1	C22—C23—C24	120.6 (2)
C12—C11—C2	125.8 (2)	C24—C23—H23	119.7
C12—C11—H11	117.1	C23—C24—C25	119.4 (2)
C11—C12—H12	116.7	C23—C24—C26	120.9 (2)
C11—C12—C13	126.6 (2)	C26—C24—C25	119.6 (2)
C13—C12—H12	116.7	C24—C25—C20	119.1 (2)
C14—C13—C12	123.2 (2)	C29—C25—C20	123.1 (2)
C14—C13—C18	117.2 (2)	C29—C25—C24	117.7 (2)
C18—C13—C12	119.6 (2)	C24—C26—H26	119.5
C13—C14—H14	119.4	C27—C26—C24	121.0 (3)
C15—C14—C13	121.3 (2)	C27—C26—H26	119.5
C15—C14—H14	119.4	C26—C27—H27	120.1
C14—C15—H15	119.4	C26—C27—C28	119.8 (3)
C14—C15—C16	121.2 (2)	C28—C27—H27	120.1
C16—C15—H15	119.4	C27—C28—H28	119.7
C15—C16—C19	120.7 (2)	C29—C28—C27	120.6 (3)
C17—C16—C15	118.0 (2)	C29—C28—H28	119.7
C17—C16—C19	121.3 (2)	C25—C29—H29	119.4
C16—C17—H17	119.5	C28—C29—C25	121.2 (2)
C18—C17—C16	121.0 (2)	C28—C29—H29	119.4
C18—C17—H17	119.5	C5—S1—C2	91.37 (12)
C13—C18—H18	119.3	C4—S6—C7	91.93 (12)
Br9—C3—C4—C5	−178.01 (19)	C18—C13—C14—C15	0.9 (4)
Br9—C3—C4—S6	0.4 (4)	C19—C16—C17—C18	179.5 (3)
C2—C3—C4—C5	1.7 (3)	C20—C7—C8—Br10	0.5 (5)
C2—C3—C4—S6	−179.9 (2)	C20—C7—C8—C5	178.2 (3)
C2—C11—C12—C13	179.7 (2)	C20—C7—S6—C4	−178.9 (2)
C3—C2—C11—C12	−172.7 (3)	C20—C21—C22—C23	−0.1 (4)
C3—C2—S1—C5	0.4 (2)	C20—C25—C29—C28	178.8 (2)
C3—C4—C5—C8	177.9 (2)	C21—C20—C25—C24	4.6 (4)
C3—C4—C5—S1	−1.4 (3)	C21—C20—C25—C29	−172.6 (2)
C3—C4—S6—C7	−177.5 (3)	C21—C22—C23—C24	3.7 (4)
C4—C5—C8—Br10	178.14 (19)	C22—C23—C24—C25	−3.0 (4)
C4—C5—C8—C7	0.3 (3)	C22—C23—C24—C26	175.9 (2)
C4—C5—S1—C2	0.6 (2)	C23—C24—C25—C20	−1.1 (4)
C5—C4—S6—C7	0.9 (2)	C23—C24—C25—C29	176.2 (2)
C7—C20—C21—C22	177.9 (2)	C23—C24—C26—C27	−176.8 (2)
C7—C20—C25—C24	−177.4 (2)	C24—C25—C29—C28	1.6 (4)
C7—C20—C25—C29	5.4 (4)	C24—C26—C27—C28	−0.4 (4)
C8—C5—S1—C2	−178.5 (3)	C25—C20—C21—C22	−4.1 (4)
C8—C7—C20—C21	−129.6 (3)	C25—C24—C26—C27	2.1 (4)
C8—C7—C20—C25	52.4 (4)	C26—C24—C25—C20	180.0 (2)
C8—C7—S6—C4	−0.8 (2)	C26—C24—C25—C29	−2.7 (4)
C11—C2—C3—Br9	−1.2 (4)	C26—C27—C28—C29	−0.8 (4)
C11—C2—C3—C4	179.2 (2)	C27—C28—C29—C25	0.1 (4)
C11—C2—S1—C5	−180.0 (2)	S1—C2—C3—Br9	178.49 (14)
C11—C12—C13—C14	1.7 (4)	S1—C2—C3—C4	−1.2 (3)
C11—C12—C13—C18	−177.5 (3)	S1—C2—C11—C12	7.7 (4)
C12—C13—C14—C15	−178.3 (3)	S1—C5—C8—Br10	−2.8 (4)
C12—C13—C18—C17	179.0 (2)	S1—C5—C8—C7	179.4 (2)
C13—C14—C15—C16	−0.9 (4)	S6—C4—C5—C8	−0.9 (3)
C14—C13—C18—C17	−0.3 (4)	S6—C4—C5—S1	179.81 (13)
C14—C15—C16—C17	0.2 (4)	S6—C7—C8—Br10	−177.24 (15)
C14—C15—C16—C19	−178.8 (2)	S6—C7—C8—C5	0.4 (3)
C15—C16—C17—C18	0.5 (4)	S6—C7—C20—C21	48.1 (3)
C16—C17—C18—C13	−0.4 (4)	S6—C7—C20—C25	−129.9 (2)

(III) 3,6-Dibromo-2-(4-tert-butylphenyl)-5-(4-methylstyryl)thieno[3,2-b]thiophene

Crystal data

C25H22Br2S2	Z = 2
Mr = 546.37	F(000) = 548
Triclinic, P1	Dx = 1.633 Mg m^−3
a = 9.5401 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1575 (17) Å	Cell parameters from 12025 reflections
c = 12.1711 (16) Å	θ = 3.1–29.1°
α = 106.933 (13)°	µ = 3.85 mm^−1
β = 98.599 (11)°	T = 100 K
γ = 92.192 (13)°	Block, yellow
V = 1111.4 (3) Å^3	0.35 × 0.3 × 0.15 mm

Data collection

Agilent SuperNova diffractometer (Single source at offset, Eos detector)	4543 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4106 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.029
Detector resolution: 15.9631 pixels mm^-1	θmax = 26.4°, θmin = 2.9°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −12→12
Tmin = 0.621, Tmax = 1.000	l = −15→15
22740 measured reflections

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.063	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0284P)^2 + 1.021P] where P = (Fo^2 + 2Fc^2)/3
4543 reflections	(Δ/σ)max = 0.001
266 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.34 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
C2	0.1667 (2)	0.4087 (2)	0.52334 (18)	0.0149 (4)
C3	0.2415 (2)	0.5007 (2)	0.48676 (17)	0.0140 (4)
C4	0.3487 (2)	0.5848 (2)	0.57443 (18)	0.0135 (4)
C5	0.3561 (2)	0.5556 (2)	0.67867 (18)	0.0149 (4)
C7	0.5323 (2)	0.7369 (2)	0.73035 (17)	0.0134 (4)
C8	0.4616 (2)	0.6421 (2)	0.76726 (18)	0.0156 (4)
C11	0.0485 (2)	0.3098 (2)	0.45728 (18)	0.0154 (4)
H11	0.0143	0.3096	0.3798	0.018*
C12	−0.0158 (2)	0.2188 (2)	0.49791 (19)	0.0163 (4)
H12	0.0209	0.2196	0.5751	0.020*
C13	−0.1367 (2)	0.1182 (2)	0.43625 (18)	0.0147 (4)
C14	−0.1847 (2)	0.0836 (2)	0.31652 (19)	0.0184 (4)
H14	−0.1379	0.1268	0.2708	0.022*
C15	−0.2997 (2)	−0.0127 (2)	0.2636 (2)	0.0195 (4)
H15	−0.3298	−0.0352	0.1818	0.023*
C16	−0.3721 (2)	−0.0775 (2)	0.3276 (2)	0.0188 (4)
C17	−0.3245 (2)	−0.0435 (2)	0.4464 (2)	0.0222 (5)
H17	−0.3719	−0.0862	0.4921	0.027*
C18	−0.2088 (2)	0.0521 (2)	0.4994 (2)	0.0212 (5)
H18	−0.1778	0.0731	0.5810	0.025*
C19	−0.4989 (2)	−0.1807 (2)	0.2693 (2)	0.0257 (5)
H19A	−0.4753	−0.2481	0.2001	0.039*
H19B	−0.5798	−0.1324	0.2460	0.039*
H19C	−0.5240	−0.2286	0.3238	0.039*
C20	0.6407 (2)	0.8514 (2)	0.79371 (18)	0.0144 (4)
C21	0.6309 (2)	0.9344 (2)	0.90533 (19)	0.0204 (5)
H21	0.5599	0.9103	0.9448	0.024*
C22	0.7237 (2)	1.0518 (2)	0.95947 (19)	0.0222 (5)
H22	0.7145	1.1068	1.0355	0.027*
C23	0.8300 (2)	1.0912 (2)	0.90537 (18)	0.0156 (4)
C24	0.8424 (2)	1.0043 (2)	0.79612 (19)	0.0174 (4)
H24	0.9167	1.0255	0.7584	0.021*
C25	0.7490 (2)	0.8872 (2)	0.74042 (18)	0.0159 (4)
H25	0.7595	0.8311	0.6651	0.019*
C26	0.9213 (2)	1.2294 (2)	0.95810 (19)	0.0181 (4)
C27	0.9335 (4)	1.2808 (3)	1.0898 (2)	0.0466 (8)
H27A	0.9785	1.2132	1.1237	0.070*
H27B	0.8384	1.2928	1.1104	0.070*
H27C	0.9915	1.3694	1.1202	0.070*
C28	0.8494 (3)	1.3340 (3)	0.9067 (3)	0.0412 (7)
H28A	0.7556	1.3468	0.9300	0.062*
H28B	0.8382	1.3003	0.8216	0.062*
H28C	0.9080	1.4224	0.9354	0.062*
C29	1.0711 (3)	1.2170 (3)	0.9299 (4)	0.0579 (10)
H29A	1.0672	1.1951	0.8455	0.087*
H29B	1.1139	1.1432	0.9567	0.087*
H29C	1.1288	1.3046	0.9692	0.087*
S1	0.23075 (6)	0.42387 (5)	0.66948 (5)	0.01670 (11)
S6	0.47053 (5)	0.71827 (5)	0.58407 (4)	0.01402 (11)
Br9	0.21007 (2)	0.51931 (2)	0.336305 (17)	0.01818 (7)
Br10	0.50454 (2)	0.61519 (2)	0.914456 (19)	0.02445 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0146 (10)	0.0139 (10)	0.0142 (10)	0.0029 (8)	0.0000 (8)	0.0020 (8)
C3	0.0143 (10)	0.0134 (10)	0.0127 (10)	0.0033 (8)	0.0010 (8)	0.0017 (8)
C4	0.0133 (10)	0.0115 (10)	0.0152 (10)	0.0006 (8)	0.0021 (8)	0.0035 (8)
C5	0.0145 (10)	0.0117 (10)	0.0172 (10)	−0.0016 (8)	−0.0002 (8)	0.0041 (8)
C7	0.0139 (10)	0.0134 (10)	0.0116 (10)	0.0015 (8)	0.0000 (8)	0.0028 (8)
C8	0.0163 (10)	0.0151 (10)	0.0139 (10)	−0.0002 (8)	−0.0004 (8)	0.0037 (8)
C11	0.0136 (10)	0.0144 (10)	0.0153 (10)	0.0008 (8)	−0.0001 (8)	0.0014 (8)
C12	0.0142 (10)	0.0162 (10)	0.0169 (10)	0.0008 (8)	−0.0007 (8)	0.0040 (8)
C13	0.0114 (9)	0.0123 (10)	0.0196 (11)	0.0010 (8)	0.0006 (8)	0.0047 (8)
C14	0.0169 (10)	0.0193 (11)	0.0194 (11)	−0.0012 (8)	0.0052 (9)	0.0056 (9)
C15	0.0165 (10)	0.0220 (11)	0.0180 (11)	0.0020 (9)	0.0011 (9)	0.0038 (9)
C16	0.0136 (10)	0.0130 (10)	0.0277 (12)	0.0001 (8)	−0.0021 (9)	0.0056 (9)
C17	0.0197 (11)	0.0218 (12)	0.0281 (12)	−0.0051 (9)	0.0007 (9)	0.0148 (10)
C18	0.0213 (11)	0.0228 (12)	0.0200 (11)	−0.0029 (9)	−0.0024 (9)	0.0106 (9)
C19	0.0183 (11)	0.0216 (12)	0.0340 (14)	−0.0050 (9)	−0.0050 (10)	0.0089 (10)
C20	0.0142 (10)	0.0108 (10)	0.0165 (10)	0.0000 (8)	−0.0026 (8)	0.0044 (8)
C21	0.0197 (11)	0.0212 (11)	0.0189 (11)	−0.0052 (9)	0.0042 (9)	0.0044 (9)
C22	0.0263 (12)	0.0196 (11)	0.0159 (11)	−0.0062 (9)	0.0024 (9)	−0.0006 (9)
C23	0.0140 (10)	0.0130 (10)	0.0188 (11)	−0.0020 (8)	−0.0041 (8)	0.0067 (8)
C24	0.0121 (10)	0.0211 (11)	0.0203 (11)	−0.0015 (8)	0.0004 (8)	0.0097 (9)
C25	0.0158 (10)	0.0168 (10)	0.0135 (10)	0.0011 (8)	0.0009 (8)	0.0030 (8)
C26	0.0176 (10)	0.0147 (10)	0.0189 (11)	−0.0047 (8)	−0.0043 (8)	0.0046 (9)
C27	0.067 (2)	0.0429 (17)	0.0190 (13)	−0.0359 (15)	−0.0120 (13)	0.0069 (12)
C28	0.0457 (16)	0.0207 (13)	0.0498 (18)	−0.0154 (11)	−0.0257 (14)	0.0181 (12)
C29	0.0241 (14)	0.0310 (16)	0.100 (3)	−0.0138 (12)	0.0164 (16)	−0.0096 (17)
S1	0.0181 (3)	0.0153 (3)	0.0159 (3)	−0.0056 (2)	−0.0012 (2)	0.0062 (2)
S6	0.0145 (2)	0.0134 (2)	0.0135 (2)	−0.00256 (19)	0.00064 (19)	0.00445 (19)
Br9	0.02011 (12)	0.02063 (12)	0.01261 (11)	−0.00192 (8)	−0.00041 (8)	0.00521 (8)
Br10	0.03123 (14)	0.02441 (13)	0.01642 (12)	−0.01005 (9)	−0.00648 (9)	0.01090 (9)

Geometric parameters (Å, º)

C2—C3	1.367 (3)	C18—H18	0.9500
C2—C11	1.449 (3)	C19—H19A	0.9800
C2—S1	1.752 (2)	C19—H19B	0.9800
C3—C4	1.410 (3)	C19—H19C	0.9800
C3—Br9	1.876 (2)	C20—C21	1.393 (3)
C4—C5	1.377 (3)	C20—C25	1.389 (3)
C4—S6	1.717 (2)	C21—H21	0.9500
C5—C8	1.415 (3)	C21—C22	1.389 (3)
C5—S1	1.727 (2)	C22—H22	0.9500
C7—C8	1.371 (3)	C22—C23	1.394 (3)
C7—C20	1.471 (3)	C23—C24	1.390 (3)
C7—S6	1.742 (2)	C23—C26	1.535 (3)
C8—Br10	1.878 (2)	C24—H24	0.9500
C11—H11	0.9500	C24—C25	1.392 (3)
C11—C12	1.337 (3)	C25—H25	0.9500
C12—H12	0.9500	C26—C27	1.519 (3)
C12—C13	1.463 (3)	C26—C28	1.518 (3)
C13—C14	1.395 (3)	C26—C29	1.521 (3)
C13—C18	1.393 (3)	C27—H27A	0.9800
C14—H14	0.9500	C27—H27B	0.9800
C14—C15	1.384 (3)	C27—H27C	0.9800
C15—H15	0.9500	C28—H28A	0.9800
C15—C16	1.394 (3)	C28—H28B	0.9800
C16—C17	1.385 (3)	C28—H28C	0.9800
C16—C19	1.509 (3)	C29—H29A	0.9800
C17—H17	0.9500	C29—H29B	0.9800
C17—C18	1.385 (3)	C29—H29C	0.9800
C3—C2—C11	127.97 (19)	H19A—C19—H19C	109.5
C3—C2—S1	110.83 (15)	H19B—C19—H19C	109.5
C11—C2—S1	121.19 (16)	C21—C20—C7	120.91 (19)
C2—C3—C4	113.44 (19)	C25—C20—C7	120.93 (19)
C2—C3—Br9	125.30 (16)	C25—C20—C21	117.95 (19)
C4—C3—Br9	121.26 (15)	C20—C21—H21	119.6
C3—C4—S6	135.45 (16)	C22—C21—C20	120.7 (2)
C5—C4—C3	112.85 (18)	C22—C21—H21	119.6
C5—C4—S6	111.68 (16)	C21—C22—H22	119.1
C4—C5—C8	112.77 (18)	C21—C22—C23	121.8 (2)
C4—C5—S1	111.53 (16)	C23—C22—H22	119.1
C8—C5—S1	135.68 (17)	C22—C23—C26	122.09 (19)
C8—C7—C20	131.33 (19)	C24—C23—C22	116.81 (19)
C8—C7—S6	111.14 (15)	C24—C23—C26	120.91 (19)
C20—C7—S6	117.42 (15)	C23—C24—H24	119.1
C5—C8—Br10	121.61 (15)	C23—C24—C25	121.86 (19)
C7—C8—C5	112.82 (19)	C25—C24—H24	119.1
C7—C8—Br10	125.41 (16)	C20—C25—C24	120.8 (2)
C2—C11—H11	117.8	C20—C25—H25	119.6
C12—C11—C2	124.5 (2)	C24—C25—H25	119.6
C12—C11—H11	117.8	C27—C26—C23	111.81 (18)
C11—C12—H12	116.5	C27—C26—C29	107.7 (2)
C11—C12—C13	127.0 (2)	C28—C26—C23	107.46 (18)
C13—C12—H12	116.5	C28—C26—C27	108.8 (2)
C14—C13—C12	123.75 (19)	C28—C26—C29	109.7 (2)
C18—C13—C12	118.85 (19)	C29—C26—C23	111.25 (19)
C18—C13—C14	117.39 (19)	C26—C27—H27A	109.5
C13—C14—H14	119.6	C26—C27—H27B	109.5
C15—C14—C13	120.8 (2)	C26—C27—H27C	109.5
C15—C14—H14	119.6	H27A—C27—H27B	109.5
C14—C15—H15	119.3	H27A—C27—H27C	109.5
C14—C15—C16	121.5 (2)	H27B—C27—H27C	109.5
C16—C15—H15	119.3	C26—C28—H28A	109.5
C15—C16—C19	121.0 (2)	C26—C28—H28B	109.5
C17—C16—C15	117.8 (2)	C26—C28—H28C	109.5
C17—C16—C19	121.1 (2)	H28A—C28—H28B	109.5
C16—C17—H17	119.6	H28A—C28—H28C	109.5
C18—C17—C16	120.8 (2)	H28B—C28—H28C	109.5
C18—C17—H17	119.6	C26—C29—H29A	109.5
C13—C18—H18	119.2	C26—C29—H29B	109.5
C17—C18—C13	121.7 (2)	C26—C29—H29C	109.5
C17—C18—H18	119.2	H29A—C29—H29B	109.5
C16—C19—H19A	109.5	H29A—C29—H29C	109.5
C16—C19—H19B	109.5	H29B—C29—H29C	109.5
C16—C19—H19C	109.5	C5—S1—C2	91.35 (10)
H19A—C19—H19B	109.5	C4—S6—C7	91.58 (10)
C2—C3—C4—C5	0.4 (3)	C19—C16—C17—C18	−179.5 (2)
C2—C3—C4—S6	−177.73 (17)	C20—C7—C8—C5	175.1 (2)
C2—C11—C12—C13	179.0 (2)	C20—C7—C8—Br10	−9.6 (3)
C3—C2—C11—C12	177.1 (2)	C20—C7—S6—C4	−175.85 (16)
C3—C2—S1—C5	0.59 (16)	C20—C21—C22—C23	−0.3 (4)
C3—C4—C5—C8	−178.68 (17)	C21—C20—C25—C24	−1.5 (3)
C3—C4—C5—S1	0.1 (2)	C21—C22—C23—C24	−2.4 (3)
C3—C4—S6—C7	177.8 (2)	C21—C22—C23—C26	172.5 (2)
C4—C5—C8—C7	0.7 (3)	C22—C23—C24—C25	3.1 (3)
C4—C5—C8—Br10	−174.92 (15)	C22—C23—C26—C27	26.8 (3)
C4—C5—S1—C2	−0.36 (17)	C22—C23—C26—C28	−92.6 (3)
C5—C4—S6—C7	−0.38 (17)	C22—C23—C26—C29	147.3 (3)
C7—C20—C21—C22	−172.5 (2)	C23—C24—C25—C20	−1.2 (3)
C7—C20—C25—C24	173.19 (19)	C24—C23—C26—C27	−158.5 (2)
C8—C5—S1—C2	178.0 (2)	C24—C23—C26—C28	82.1 (3)
C8—C7—C20—C21	−40.0 (3)	C24—C23—C26—C29	−38.0 (3)
C8—C7—C20—C25	145.4 (2)	C25—C20—C21—C22	2.2 (3)
C8—C7—S6—C4	0.75 (16)	C26—C23—C24—C25	−171.87 (19)
C11—C2—C3—C4	178.58 (19)	S1—C2—C3—C4	−0.7 (2)
C11—C2—C3—Br9	−1.3 (3)	S1—C2—C3—Br9	179.46 (11)
C11—C2—S1—C5	−178.72 (17)	S1—C2—C11—C12	−3.7 (3)
C11—C12—C13—C14	13.6 (3)	S1—C5—C8—C7	−177.65 (18)
C11—C12—C13—C18	−166.6 (2)	S1—C5—C8—Br10	6.8 (3)
C12—C13—C14—C15	179.9 (2)	S6—C4—C5—C8	−0.1 (2)
C12—C13—C18—C17	179.6 (2)	S6—C4—C5—S1	178.65 (10)
C13—C14—C15—C16	0.6 (3)	S6—C7—C8—C5	−0.9 (2)
C14—C13—C18—C17	−0.6 (3)	S6—C7—C8—Br10	174.46 (12)
C14—C15—C16—C17	−0.7 (3)	S6—C7—C20—C21	135.75 (18)
C14—C15—C16—C19	179.0 (2)	S6—C7—C20—C25	−38.8 (3)
C15—C16—C17—C18	0.1 (3)	Br9—C3—C4—C5	−179.72 (15)
C16—C17—C18—C13	0.5 (4)	Br9—C3—C4—S6	2.1 (3)
C18—C13—C14—C15	0.0 (3)