4-Benzyl­idene-3,4-dihydro-1λ4-cyclo­penta­[2,1-b:3,4-b′]dithio­phene at 120 K

Howie, R.A.; Wardell, J.L.

doi:10.1107/S1600536806001346

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 2| February 2006| Pages o659-o661

https://doi.org/10.1107/S1600536806001346

4-Benzylidene-3,4-dihydro-1λ⁴-cyclopenta[2,1-b:3,4-b′]dithiophene at 120 K

R. Alan Howie ^a ^* and James L. Wardell ^b

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, and ^bDepartamento de Química Inorgânica, Instituto de Química, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: r.a.howie@abdn.ac.uk

(Received 11 January 2006; accepted 12 January 2006; online 18 January 2006)

The title compound, C₁₆H₁₀S₂, is a further example of a 3,3′-bridged 2,2′-dithiophene. As in comparable members of this series of compounds, the monoatomic 3,3′-bridge constrains the tricyclic heterocyclic ring system to be essentially planar with, in this case, an S—C—C—S torsion angle of 2.3 (4)°.

Comment

The title compound, (I), was synthesized with a view to investigating its potential as a ligand. A search of the Cambridge Structural Database (Allen, 2002 ), accessed by means of the Chemical Database Service of the EPSRC (Fletcher et al., 1996 ), revealed, however, the presence of known structures for a number of 3,3′-bridged 2,2′-dithiophenes, (II)–(VI) (Koster et al., 1970 ; Pilati, 1995 ) analogous to (I). It is in relation to these, especially the series (II)–(VI) described by Pilati (1995), that the structure of (I) is discussed here.

The molecule of (I) is shown in Fig. 1 and selected bond lengths and angles are given in Table 1. In addition to the values given in the Table, and noting the C5—C6—C7 angle of 104.19 (19)°, the remaining internal C—C—C angles of the five-membered rings are in the range 108.3 (2)–112.4 (2)°. The C—C—S internal angles, in the range 112.15 (17)–113.09 (19)°, show less variation. The bond lengths and angles in the phenyl group in the ranges 1.380 (3)–1.395 (3) Å and 118.0 (2)–121.5 (2)°, respectively, are unexceptional. The torsion angles about the C1—C2 bond are a clear indication of the planar nature of the dithiophene ring system. The torsion angles about the C10—C11 bond, on the other hand, indicate a tilt of the phenyl group relative to the dithiophene group which amounts to a dihedral angle between their least squares planes of 44.38 (6)°.

A feature of the molecule of (I) is the difference between the S1—C1 and S2—C2 bond lengths [1.712 (2) and 1.711 (2) Å, respectively] and the S1—C9 and S2—C3 bond lengths [1.734 (3) and 1.727 (3) Å, respectively]. Pilati (1995) has noted a similar disparity in S—C bond lengths, in the same sense for (II) and, although less marked, for (III) but in the opposite sense for (IV)–(VI) (see Table 2). Also evident from the torsion-angle data given in Table 2 is the planarity of the dithiophene ring system in the case of (II) and (III), now along with (I), which is not the case for (IV)–(VI). It is clear, therefore, that the monoatomic 3,3′ bridge in (I)–(III) as opposed to the polyatomic bridges in (IV)–(VI) is the key factor in creating the structural differences between the two classes of compound and is largely independent of the nature of the species providing the monoatomic bridge.

The molecules of (I) are found in layers parallel to (100) (Fig. 2) within which there are two significant intermolecular contacts. The first of these is a π–π interaction arising from the overlap of the dithiophene ring systems in pairs, creating interactions involving the rings with centroid Cg1 defined by C1/C2/C5–C7. For this interaction, Cg1⋯Cg1ⁱⁱⁱ [symmetry code: (iii) −x, y, −z + $[{1\over 2}]$ ], the distance between the ring centroids, the perpendicular distance of the centroid of one ring to the least-squares plane of the other ring of the pair and the lateral displacement or slippage of the rings relative to one another are 3.829, 3.467 and 1.625 Å, respectively. The second interaction is a C—H⋯π contact of the form C8—H8⋯Cg2ⁱ where Cg2 is the centroid of the ring defined by C2/S2/C3–C5 [symmetry code: (i) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ]. Here the C—H, H⋯Cg, the perpendicular distance of the H atom from the l.s. plane of the ring and the C⋯Cg distances are 0.95, 2.750, 2.706 and 3.650 Å, respectively, and the C—H⋯Cg angle is 158°. Stacking of these layers in the direction of a produces a further π–π interaction between pairs of phenyl rings, C11–C16 with centroid Cg3, of the form Cg3⋯Cg3ⁱⁱ (Fig. 3) [symmetry code: (ii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z] for which the distance between the ring centroids, the perpendicular distance of the centroid of one ring to the least-squares plane of the other ring of the pair and the lateral displacement or slippage of the rings relative to one another are 3.617, 3.607 and 0.269 Å, respectively.

Figure 1
The molecular structure of (I)

. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2
A layer of molecules of (I)

parallel to (100) and centred on x = ¼. For clarity, the phenyl group (C11–C16) is shown in thin line outline and only the H atoms involved in C—H⋯π contacts are shown as small spheres of arbitrary radii. Dashed lines represent intermolecular contacts. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (v) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (vi) x, −y + 1, z + $[{1\over 2}]$ ; (vii) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (viii) x, y, z + 1.]

Figure 3
A section through the structure of (I)

parallel to (010) and centred on y = $[1\over4]$ , showing interlayer π⋯π contacts (dashed lines). Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted. [Symmetry codes: (iii) −x, y, −z + $[{1\over 2}]$ ; (v) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (ix) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .]

Experimental

To a solution of 4H-cyclopenta[2,1-b:3,4-b′]dithiophene (2.0 g, 11.2 mmol), (II) (Kraak et al., 1968 ), in Et₂O (25 ml) at 273 K was added dropwise by syringe a solution of BuLi (11.3 mmol) in hexane. The reaction mixture was stirred at 273 K for 1 h after addition was complete. A solution of PhCHO (1.3 g, 12 mmol) in Et₂O (10 ml) was then slowly added. The reaction mixture was refluxed for 20 min., saturated aqueous NH₄Cl solution (30 ml) added, the organic layer collected, washed with water and dried over MgSO₄, and rotary evaporated. The residue was recrystallized successively from EtOH and MeCN. The orange-red crystals used in the X-ray crystal structure determination were grown slowly from MeCN solution (m.p. 408–410 K).

Crystal data

C₁₆H₁₀S₂
M_r = 266.36
Monoclinic, C 2/c
a = 19.618 (2) Å
b = 10.4720 (8) Å
c = 12.0157 (12) Å
β = 91.525 (4)°
V = 2467.6 (4) Å³
Z = 8
D_x = 1.434 Mg m⁻³
Mo Kα radiation
Cell parameters from 2794 reflections
θ = 2.9–27.5°
μ = 0.41 mm⁻¹
T = 120 (2) K
Plate, orange–red
0.28 × 0.22 × 0.03 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.662, T_max = 0.990
11902 measured reflections
2815 independent reflections
1836 reflections with I > 2σ(I)
R_int = 0.056
θ_max = 27.5°
h = −25 → 25
k = −13 → 12
l = −14 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.114
S = 1.03
2815 reflections
163 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0487P)² + 1.7202P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

S1—C1	1.712 (2)
S1—C9	1.734 (3)
S2—C2	1.711 (2)
S2—C3	1.727 (3)
C1—C7	1.386 (3)
C1—C2	1.449 (3)
C2—C5	1.383 (3)
C3—C4	1.367 (3)
C4—C5	1.426 (3)
C5—C6	1.488 (3)
C6—C10	1.348 (3)
C6—C7	1.479 (3)
C7—C8	1.420 (3)
C8—C9	1.356 (3)
C10—C11	1.465 (3)

C1—S1—C9	90.63 (12)
C2—S2—C3	90.72 (11)
C2—C1—S1	139.53 (18)
C1—C2—S2	137.92 (19)
C4—C5—C6	139.2 (2)
C7—C6—C5	104.19 (19)
C8—C7—C6	138.1 (2)
C6—C10—C11	127.7 (2)

C7—C1—C2—C5	−0.7 (3)
S1—C1—C2—S2	2.3 (4)
C6—C10—C11—C12	142.3 (2)
C6—C10—C11—C16	−40.9 (4)

Table 2
Summary of S—C distances (Å) and absolute values of selected torsion angles (°) for (I–VI)

For (II–IV), values and the associated su's have been averaged over all molecules in the asymmetric unit. In all cases S—C distances, according to type, have been averaged, in addition, over the two thiophene rings. Values for (II–VI) were obtained from the data of Pilati (1995).

Compound	S1—C1	S1—C9	S1—C1—C2—S2	C7—C1—C2—C5
(I)	1.712 (2)	1.730 (3)	2.3 (4)	0.7 (3)
(II)	1.713 (2)	1.726 (2)	4.4 (5)	0.2 (3)
(III)	1.709 (2)	1.716 (2)	2.6 (4)	0.9 (3)
(IV)	1.729 (1)	1.705 (2)	9.7 (2)	10.8 (3)
(V)	1.728 (1)	1.704 (2)	109.6 (1)	111.7 (2)
(VI)	1.728 (2)	1.708 (2)	56.8 (2)	61.3 (3)

In the final stages of refinement H atoms were placed in calculated positions, with C—H = 0.95 Å, and refined with a riding model, with U_iso(H) = 1.2U_eq(C)

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806001346/lh6580sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806001346/lh6580Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

4-Benzylidene-3,4-dihydro-1λ⁴-cyclopenta[2,1 - b:3,4 - b']dithiophene top

Crystal data top

C₁₆H₁₀S₂	F(000) = 1104
M_r = 266.36	D_x = 1.434 Mg m⁻³
Monoclinic, C2/c	Melting point = 408–410 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 19.618 (2) Å	Cell parameters from 2794 reflections
b = 10.4720 (8) Å	θ = 2.9–27.5°
c = 12.0157 (12) Å	µ = 0.41 mm⁻¹
β = 91.525 (4)°	T = 120 K
V = 2467.6 (4) Å³	Plate, orange–red
Z = 8	0.28 × 0.22 × 0.03 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	2815 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	1836 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.7°
φ and ω scans	h = −25→25
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→12
T_min = 0.662, T_max = 0.990	l = −14→15
11902 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0487P)² + 1.7202P] where P = (F_o² + 2F_c²)/3
2815 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Special details top

Experimental. Unit cell determined with DIRAX (Duisenberg, 1992; Duisenberg et al. 2000) but refined with the DENZO/COLLECT HKL package.

Refs as: Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96. Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000). J. Appl. Cryst. 33, 893–898.

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

-4.5802 (74) x + 6.7513 (30) y + 8.8179 (28) z = 2.2432 (28)

* -0.0070 (0.0011) S1 * 0.0370 (0.0011) S2 * 0.0328 (0.0020) C1 * 0.0653 (0.0020) C2 * -0.0660 (0.0018) C3 * -0.0676 (0.0019) C4 * 0.0356 (0.0020) C5 * 0.0251 (0.0019) C6 * -0.0007 (0.0020) C7 * -0.0313 (0.0020) C8 * -0.0476 (0.0019) C9 * 0.0246 (0.0015) C10 0.1674 (0.0030) C11 - 0.5633 (0.0034) C12 1.0795 (0.0030) C16

Rms deviation of fitted atoms = 0.0423

-5.7121 (184) x - 0.7716 (114) y + 11.5500 (35) z = 0.8846 (33)

Angle to previous plane (with approximate e.s.d.) = 44.38 (0.06)

* -0.0118 (0.0017) C11 * 0.0129 (0.0018) C12 * -0.0036 (0.0019) C13 * -0.0067 (0.0018) C14 * 0.0076 (0.0018) C15 * 0.0017 (0.0017) C16

Rms deviation of fitted atoms = 0.0084

-4.3812 (169) x + 6.5423 (86) y + 9.0585 (91) z = 2.2968 (68)

Angle to previous plane (with approximate e.s.d.) = 42.89 (0.08)

* -0.0023 (0.0011) S1 * 0.0056 (0.0013) C1 * -0.0070 (0.0015) C7 * 0.0049 (0.0015) C8 * -0.0013 (0.0014) C9

Rms deviation of fitted atoms = 0.0047

-4.6361 (217) x + 6.5709 (91) y + 8.9870 (90) z = 2.2174 (71)

Angle to previous plane (with approximate e.s.d.) = 0.84 (0.16)

* 0.0002 (0.0014) C1 * 0.0076 (0.0014) C2 * -0.0117 (0.0014) C5 * 0.0111 (0.0013) C6 * -0.0072 (0.0014) C7

Rms deviation of fitted atoms = 0.0086

-5.5056 (169) x + 6.9517 (74) y + 8.4164 (95) z = 2.1095 (55)

Angle to previous plane (with approximate e.s.d.) = 4.31 (0.16)

* 0.0068 (0.0010) S2 * -0.0124 (0.0013) C2 * -0.0007 (0.0013) C3 * -0.0068 (0.0015) C4 * 0.0132 (0.0014) C5

Rms deviation of fitted atoms = 0.0092

-4.3812 (169) x + 6.5423 (86) y + 9.0585 (91) z = 2.2968 (68)

Angle to previous plane (with approximate e.s.d.) = 5.07 (0.15)

* -0.0023 (0.0011) S1 * 0.0056 (0.0013) C1 * -0.0070 (0.0015) C7 * 0.0049 (0.0015) C8 * -0.0013 (0.0014) C9

Rms deviation of fitted atoms = 0.0047

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.41276 (3)	0.34681 (6)	0.20246 (6)	0.0337 (2)
S2	0.30609 (3)	0.56535 (6)	−0.01529 (6)	0.0319 (2)
C1	0.33082 (12)	0.3631 (2)	0.1519 (2)	0.0244 (5)
C2	0.29170 (12)	0.4422 (2)	0.07472 (19)	0.0244 (5)
C3	0.22272 (12)	0.5580 (2)	−0.0646 (2)	0.0292 (6)
H3	0.2046	0.6124	−0.1214	0.035*
C4	0.18543 (13)	0.4658 (2)	−0.01358 (19)	0.0273 (6)
H4	0.1389	0.4479	−0.0312	0.033*
C5	0.22499 (12)	0.3996 (2)	0.06933 (19)	0.0234 (5)
C6	0.21796 (12)	0.2908 (2)	0.14779 (18)	0.0235 (5)
C7	0.28757 (12)	0.2722 (2)	0.19526 (19)	0.0241 (5)
C8	0.32155 (13)	0.1898 (2)	0.2725 (2)	0.0290 (6)
H8	0.2998	0.1230	0.3115	0.035*
C9	0.38882 (14)	0.2184 (2)	0.2837 (2)	0.0339 (6)
H9	0.4197	0.1727	0.3313	0.041*
C10	0.16312 (12)	0.2201 (2)	0.17339 (19)	0.0269 (6)
H10	0.1716	0.1487	0.2205	0.032*
C11	0.09204 (12)	0.2404 (2)	0.13714 (19)	0.0265 (5)
C12	0.05003 (13)	0.1370 (2)	0.1116 (2)	0.0329 (6)
H12	0.0678	0.0528	0.1172	0.039*
C13	−0.01742 (14)	0.1552 (2)	0.0780 (2)	0.0373 (6)
H13	−0.0450	0.0836	0.0588	0.045*
C14	−0.04489 (13)	0.2764 (2)	0.0723 (2)	0.0350 (6)
H14	−0.0911	0.2887	0.0492	0.042*
C15	−0.00416 (14)	0.3798 (2)	0.1006 (2)	0.0357 (6)
H15	−0.0228	0.4635	0.0982	0.043*
C16	0.06354 (13)	0.3624 (2)	0.1324 (2)	0.0318 (6)
H16	0.0909	0.4344	0.1512	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0298 (4)	0.0324 (4)	0.0383 (4)	−0.0003 (3)	−0.0080 (3)	0.0038 (3)
S2	0.0299 (4)	0.0273 (3)	0.0384 (4)	−0.0003 (3)	0.0000 (3)	0.0092 (3)
C1	0.0238 (13)	0.0228 (11)	0.0264 (13)	0.0026 (10)	−0.0042 (10)	−0.0029 (10)
C2	0.0290 (14)	0.0195 (11)	0.0247 (12)	0.0005 (10)	0.0008 (11)	−0.0015 (10)
C3	0.0311 (15)	0.0261 (12)	0.0303 (13)	0.0063 (10)	−0.0019 (11)	0.0067 (11)
C4	0.0291 (14)	0.0270 (12)	0.0257 (13)	0.0020 (10)	−0.0004 (11)	−0.0024 (10)
C5	0.0252 (14)	0.0204 (11)	0.0244 (12)	0.0015 (10)	−0.0001 (10)	−0.0030 (10)
C6	0.0292 (14)	0.0200 (11)	0.0211 (12)	0.0023 (10)	−0.0025 (11)	−0.0030 (10)
C7	0.0295 (14)	0.0208 (11)	0.0220 (12)	0.0001 (10)	−0.0022 (11)	−0.0032 (10)
C8	0.0352 (16)	0.0245 (12)	0.0270 (13)	0.0006 (11)	−0.0029 (12)	−0.0001 (10)
C9	0.0411 (17)	0.0270 (13)	0.0332 (15)	0.0042 (11)	−0.0081 (13)	0.0015 (11)
C10	0.0337 (15)	0.0220 (12)	0.0248 (13)	−0.0013 (10)	−0.0008 (11)	0.0010 (10)
C11	0.0290 (14)	0.0289 (12)	0.0217 (12)	−0.0010 (11)	0.0011 (11)	0.0050 (11)
C12	0.0324 (16)	0.0287 (13)	0.0375 (15)	−0.0017 (11)	0.0010 (12)	0.0067 (12)
C13	0.0299 (16)	0.0389 (15)	0.0432 (16)	−0.0067 (12)	0.0002 (13)	0.0042 (13)
C14	0.0305 (15)	0.0448 (16)	0.0296 (14)	0.0020 (12)	0.0012 (12)	0.0048 (12)
C15	0.0340 (16)	0.0348 (14)	0.0386 (15)	0.0079 (12)	0.0077 (13)	0.0038 (12)
C16	0.0331 (16)	0.0290 (13)	0.0336 (15)	−0.0013 (11)	0.0065 (12)	0.0007 (11)

Geometric parameters (Å, º) top

S1—C1	1.712 (2)	C8—H8	0.9500
S1—C9	1.734 (3)	C9—H9	0.9500
S2—C2	1.711 (2)	C10—C11	1.465 (3)
S2—C3	1.727 (3)	C10—H10	0.9500
C1—C7	1.386 (3)	C11—C12	1.390 (3)
C1—C2	1.449 (3)	C11—C16	1.395 (3)
C2—C5	1.383 (3)	C12—C13	1.386 (4)
C3—C4	1.367 (3)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.380 (3)
C4—C5	1.426 (3)	C13—H13	0.9500
C4—H4	0.9500	C14—C15	1.382 (4)
C5—C6	1.488 (3)	C14—H14	0.9500
C6—C10	1.348 (3)	C15—C16	1.384 (3)
C6—C7	1.479 (3)	C15—H15	0.9500
C7—C8	1.420 (3)	C16—H16	0.9500
C8—C9	1.356 (3)

C1—S1—C9	90.63 (12)	C7—C8—H8	124.1
C2—S2—C3	90.72 (11)	C8—C9—S1	113.09 (19)
C7—C1—C2	108.3 (2)	C8—C9—H9	123.5
C7—C1—S1	112.15 (17)	S1—C9—H9	123.5
C2—C1—S1	139.53 (18)	C6—C10—C11	127.7 (2)
C5—C2—C1	109.3 (2)	C6—C10—H10	116.1
C5—C2—S2	112.67 (18)	C11—C10—H10	116.1
C1—C2—S2	137.92 (19)	C12—C11—C16	118.0 (2)
C4—C3—S2	113.02 (18)	C12—C11—C10	120.5 (2)
C4—C3—H3	123.5	C16—C11—C10	121.5 (2)
S2—C3—H3	123.5	C13—C12—C11	120.9 (2)
C3—C4—C5	111.7 (2)	C13—C12—H12	119.6
C3—C4—H4	124.2	C11—C12—H12	119.6
C5—C4—H4	124.2	C14—C13—C12	120.6 (2)
C2—C5—C4	111.9 (2)	C14—C13—H13	119.7
C2—C5—C6	108.7 (2)	C12—C13—H13	119.7
C4—C5—C6	139.2 (2)	C13—C14—C15	119.0 (3)
C10—C6—C7	125.0 (2)	C13—C14—H14	120.5
C10—C6—C5	130.8 (2)	C15—C14—H14	120.5
C7—C6—C5	104.19 (19)	C14—C15—C16	120.6 (2)
C1—C7—C8	112.4 (2)	C14—C15—H15	119.7
C1—C7—C6	109.5 (2)	C16—C15—H15	119.7
C8—C7—C6	138.1 (2)	C15—C16—C11	120.8 (2)
C9—C8—C7	111.7 (2)	C15—C16—H16	119.6
C9—C8—H8	124.1	C11—C16—H16	119.6

C7—C1—C2—C5	−0.7 (3)	C6—C10—C11—C12	142.3 (2)
S1—C1—C2—S2	2.3 (4)	C6—C10—C11—C16	−40.9 (4)

Summary of S—C distances (Å) and absolute values of selected torsion angles (°) for (I–VI). For (II–IV) values, and the associated su's, have been averaged over all molecules in the asymmetric unit. In all cases S—C distances, according to type, have been averaged, in addition, over the two thiophene rings. Values for (II-VI) obtained from the data of Pilati (1995). top

Compound	S1—C1	S1—C9	S1—C1—C2—S2	C7—C1—C2—C5
(I)	1.712 (2)	1.730 (3)	2.3 (4)	0.7 (3)
(II)	1.713 (2)	1.726 (2)	4.4 (5)	0.2 (3)
(III)	1.709 (2)	1.716 (2)	2.6 (4)	0.9 (3)
(IV)	1.729 (1)	1.705 (2)	9.7 (2)	10.8 (3)
(V)	1.728 (1)	1.704 (2)	109.6 (1)	111.7 (2)
(VI)	1.728 (2)	1.708 (2)	56.8 (2)	61.3 (3)

Acknowledgements

The authors acknowledge the use of the Chemical Database Service at Daresbury and the X-ray crystallographic service at Southampton, England, both provided by the EPSRC.

References

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