Diethyl 3,4-dimethyl-thieno[2,3-b]thio-phene-2,5-dicarboxyl-ate.

In the title compound, C14H16O4S2, the thieno[2,3-b]thio-phene ring systems are planar [maximum deviation = 0.008 (2) Å]. The mol-ecular conformation is stabilized by intra-molecular C-H⋯O hydrogen bonds, while the crystal packing is stabilized by C-H⋯O, C-H⋯π and π-π stacking [centroid-centroid distance = 3.6605 (14) Å] inter-actions, which lead to supra-molecular layers in the ab plane.

Related literature

For the use of thienthio­phenes as versatile precursors for the synthesis of various heterocycles, see: Mabkhot et al. (2010 ▶, 2012 ▶); Litvinov (2005 ▶). For their industrial applications, see: Lee & Sotzing (2001 ▶); Heeney et al. (2005 ▶); Gather et al. (2008 ▶); He et al. (2009 ▶). For pharmaceutical values of thieno[2,3-b]thio­phenes, see: Jarak et al. (2006 ▶); Egbertson et al. (1999 ▶). For bond lengths and bond angles in similar compounds, see: Umadevi et al. (2009 ▶); Gunasekaran et al. (2009 ▶); Wang et al. (2008 ▶). For the synthesis of the title compound, see: Comel & Kirsch (2001a ▶,b ▶). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C14H16O4S2

M = 312.39

Triclinic,

a = 7.3497 (3) Å

b = 8.4720 (4) Å

c = 12.8629 (5) Å

α = 102.770 (3)°

β = 99.545 (3)°

γ = 107.779 (4)°

V = 719.96 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.38 mm−1

T = 123 K

0.30 × 0.08 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.966, T max = 1.000

6901 measured reflections

3486 independent reflections

2661 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.106

S = 1.04

3486 reflections

185 parameters

H-atom parameters constrained

Δρmax = 0.53 e Å−3

Δρmin = −0.34 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681204593X/tk5168sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204593X/tk5168Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681204593X/tk5168Isup3.cml

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

C14H16O4S2	Z = 2
Mr = 312.39	F(000) = 328
Triclinic, P1	Dx = 1.441 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3497 (3) Å	Cell parameters from 2806 reflections
b = 8.4720 (4) Å	θ = 3.2–29.4°
c = 12.8629 (5) Å	µ = 0.38 mm−1
α = 102.770 (3)°	T = 123 K
β = 99.545 (3)°	Rod, colourless
γ = 107.779 (4)°	0.30 × 0.08 × 0.06 mm
V = 719.96 (6) Å3

Oxford Diffraction Xcalibur Eos diffractometer	3486 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2661 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 16.0727 pixels mm-1	θmax = 29.5°, θmin = 3.2°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
Tmin = 0.966, Tmax = 1.000	l = −17→17
6901 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0365P)2 + 0.4173P] where P = (Fo2 + 2Fc2)/3
3486 reflections	(Δ/σ)max = 0.002
185 parameters	Δρmax = 0.53 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
S1	0.19179 (8)	0.66605 (7)	0.37995 (4)	0.0197 (2)
S2	0.42025 (8)	0.92886 (7)	0.61200 (4)	0.0196 (2)
O1	0.6436 (2)	0.8879 (2)	0.90039 (13)	0.0290 (5)
O2	0.6126 (2)	1.1054 (2)	0.83495 (12)	0.0258 (5)
O3	0.0104 (2)	0.1626 (2)	0.26378 (12)	0.0222 (5)
O4	−0.0238 (2)	0.3735 (2)	0.19133 (13)	0.0273 (5)
C1	0.3073 (3)	0.7294 (3)	0.51711 (17)	0.0180 (6)
C2	0.4771 (3)	0.8283 (3)	0.71229 (17)	0.0198 (7)
C3	0.4109 (3)	0.6525 (3)	0.67430 (17)	0.0179 (6)
C4	0.3115 (3)	0.5931 (3)	0.55924 (17)	0.0167 (6)
C5	0.2161 (3)	0.4277 (3)	0.47680 (17)	0.0173 (6)
C6	0.1453 (3)	0.4496 (3)	0.37738 (18)	0.0187 (6)
C7	0.4314 (3)	0.5352 (3)	0.74333 (19)	0.0241 (7)
C8	0.2012 (3)	0.2576 (3)	0.49704 (18)	0.0215 (7)
C9	0.5860 (3)	0.9392 (3)	0.82492 (18)	0.0208 (7)
C10	0.7119 (4)	1.2220 (3)	0.94621 (19)	0.0270 (8)
C11	0.7189 (4)	1.3989 (3)	0.9461 (2)	0.0333 (8)
C12	0.0360 (3)	0.3267 (3)	0.26830 (18)	0.0200 (7)
C13	−0.0980 (3)	0.0358 (3)	0.15737 (18)	0.0238 (7)
C14	−0.1327 (4)	−0.1397 (3)	0.1742 (2)	0.0339 (8)
H7A	0.51440	0.60450	0.81710	0.0360*
H7B	0.49260	0.45630	0.70920	0.0360*
H7C	0.30070	0.46780	0.74890	0.0360*
H8A	0.09500	0.16430	0.43900	0.0320*
H8B	0.17240	0.25770	0.56880	0.0320*
H8C	0.32650	0.23930	0.49660	0.0320*
H10A	0.84740	1.22180	0.96810	0.0320*
H10B	0.63870	1.18320	0.99940	0.0320*
H11A	0.79250	1.43660	0.89370	0.0500*
H11B	0.78470	1.47890	1.02010	0.0500*
H11C	0.58420	1.39800	0.92450	0.0500*
H13A	−0.02020	0.05130	0.10210	0.0290*
H13B	−0.22530	0.04930	0.13110	0.0290*
H14A	−0.00580	−0.14950	0.20290	0.0510*
H14B	−0.20110	−0.22920	0.10380	0.0510*
H14C	−0.21400	−0.15490	0.22700	0.0510*

	U11	U22	U33	U12	U13	U23
S1	0.0227 (3)	0.0181 (3)	0.0164 (3)	0.0062 (2)	0.0022 (2)	0.0049 (2)
S2	0.0231 (3)	0.0171 (3)	0.0170 (3)	0.0065 (2)	0.0030 (2)	0.0041 (2)
O1	0.0353 (9)	0.0283 (10)	0.0183 (8)	0.0094 (8)	−0.0007 (7)	0.0051 (7)
O2	0.0300 (9)	0.0246 (10)	0.0164 (8)	0.0088 (7)	−0.0017 (7)	0.0003 (7)
O3	0.0253 (8)	0.0173 (9)	0.0181 (8)	0.0045 (7)	0.0002 (6)	0.0020 (6)
O4	0.0327 (9)	0.0233 (10)	0.0199 (8)	0.0064 (7)	−0.0002 (7)	0.0045 (7)
C1	0.0162 (10)	0.0191 (12)	0.0167 (10)	0.0050 (9)	0.0030 (8)	0.0037 (9)
C2	0.0196 (11)	0.0256 (13)	0.0152 (10)	0.0092 (9)	0.0043 (8)	0.0063 (9)
C3	0.0156 (10)	0.0218 (12)	0.0186 (11)	0.0074 (9)	0.0055 (8)	0.0083 (9)
C4	0.0130 (10)	0.0188 (12)	0.0187 (10)	0.0050 (8)	0.0053 (8)	0.0063 (9)
C5	0.0157 (10)	0.0173 (12)	0.0201 (11)	0.0065 (9)	0.0059 (8)	0.0061 (9)
C6	0.0171 (10)	0.0175 (12)	0.0199 (11)	0.0054 (9)	0.0048 (8)	0.0033 (9)
C7	0.0279 (12)	0.0230 (13)	0.0210 (11)	0.0095 (10)	0.0029 (9)	0.0074 (10)
C8	0.0225 (11)	0.0188 (12)	0.0218 (11)	0.0063 (9)	0.0035 (9)	0.0063 (9)
C9	0.0164 (11)	0.0251 (13)	0.0203 (11)	0.0071 (9)	0.0053 (9)	0.0052 (9)
C10	0.0321 (13)	0.0239 (14)	0.0191 (12)	0.0081 (10)	0.0013 (10)	0.0010 (10)
C11	0.0400 (15)	0.0257 (15)	0.0266 (13)	0.0098 (12)	−0.0010 (11)	0.0023 (11)
C12	0.0172 (11)	0.0207 (12)	0.0200 (11)	0.0046 (9)	0.0058 (8)	0.0041 (9)
C13	0.0221 (11)	0.0187 (13)	0.0211 (11)	0.0023 (9)	0.0009 (9)	−0.0025 (9)
C14	0.0379 (15)	0.0217 (14)	0.0345 (15)	0.0076 (11)	0.0043 (11)	0.0012 (11)

S1—C1	1.711 (2)	C10—C11	1.484 (4)
S1—C6	1.751 (3)	C13—C14	1.501 (4)
S2—C1	1.712 (2)	C7—H7A	0.9800
S2—C2	1.758 (2)	C7—H7B	0.9800
O1—C9	1.214 (3)	C7—H7C	0.9800
O2—C9	1.334 (3)	C8—H8A	0.9800
O2—C10	1.465 (3)	C8—H8B	0.9800
O3—C12	1.331 (3)	C8—H8C	0.9800
O3—C13	1.459 (3)	C10—H10A	0.9900
O4—C12	1.211 (3)	C10—H10B	0.9900
C1—C4	1.386 (3)	C11—H11A	0.9800
C2—C3	1.360 (3)	C11—H11B	0.9800
C2—C9	1.475 (3)	C11—H11C	0.9800
C3—C4	1.437 (3)	C13—H13A	0.9900
C3—C7	1.495 (3)	C13—H13B	0.9900
C4—C5	1.441 (3)	C14—H14A	0.9800
C5—C6	1.373 (3)	C14—H14B	0.9800
C5—C8	1.495 (4)	C14—H14C	0.9800
C6—C12	1.472 (3)
C1—S1—C6	89.57 (11)	C3—C7—H7C	109.00
C1—S2—C2	89.39 (11)	H7A—C7—H7B	109.00
C9—O2—C10	114.48 (17)	H7A—C7—H7C	109.00
C12—O3—C13	115.57 (17)	H7B—C7—H7C	109.00
S1—C1—S2	132.34 (15)	C5—C8—H8A	109.00
S1—C1—C4	113.81 (17)	C5—C8—H8B	109.00
S2—C1—C4	113.85 (16)	C5—C8—H8C	109.00
S2—C2—C3	113.92 (16)	H8A—C8—H8B	110.00
S2—C2—C9	118.18 (18)	H8A—C8—H8C	109.00
C3—C2—C9	127.9 (2)	H8B—C8—H8C	109.00
C2—C3—C4	111.0 (2)	O2—C10—H10A	110.00
C2—C3—C7	124.9 (2)	O2—C10—H10B	110.00
C4—C3—C7	124.1 (2)	C11—C10—H10A	110.00
C1—C4—C3	111.8 (2)	C11—C10—H10B	110.00
C1—C4—C5	112.16 (19)	H10A—C10—H10B	108.00
C3—C4—C5	136.0 (2)	C10—C11—H11A	109.00
C4—C5—C6	110.3 (2)	C10—C11—H11B	109.00
C4—C5—C8	124.45 (19)	C10—C11—H11C	109.00
C6—C5—C8	125.3 (2)	H11A—C11—H11B	109.00
S1—C6—C5	114.18 (18)	H11A—C11—H11C	109.00
S1—C6—C12	113.10 (17)	H11B—C11—H11C	109.00
C5—C6—C12	132.7 (2)	O3—C13—H13A	110.00
O1—C9—O2	123.4 (2)	O3—C13—H13B	110.00
O1—C9—C2	125.1 (2)	C14—C13—H13A	110.00
O2—C9—C2	111.59 (19)	C14—C13—H13B	110.00
O2—C10—C11	108.25 (19)	H13A—C13—H13B	109.00
O3—C12—O4	124.3 (2)	C13—C14—H14A	109.00
O3—C12—C6	113.56 (19)	C13—C14—H14B	109.00
O4—C12—C6	122.1 (2)	C13—C14—H14C	109.00
O3—C13—C14	106.76 (18)	H14A—C14—H14B	110.00
C3—C7—H7A	109.00	H14A—C14—H14C	109.00
C3—C7—H7B	109.00	H14B—C14—H14C	109.00
C6—S1—C1—S2	179.7 (2)	C9—C2—C3—C7	2.3 (4)
C6—S1—C1—C4	0.3 (2)	S2—C2—C9—O1	−175.95 (19)
C1—S1—C6—C5	−0.3 (2)	S2—C2—C9—O2	4.8 (3)
C1—S1—C6—C12	179.25 (18)	C3—C2—C9—O1	4.7 (4)
C2—S2—C1—S1	−179.2 (2)	C3—C2—C9—O2	−174.6 (2)
C2—S2—C1—C4	0.3 (2)	C2—C3—C4—C1	−0.5 (3)
C1—S2—C2—C3	−0.6 (2)	C2—C3—C4—C5	179.2 (3)
C1—S2—C2—C9	180.0 (2)	C7—C3—C4—C1	177.4 (2)
C10—O2—C9—O1	−2.0 (3)	C7—C3—C4—C5	−3.0 (4)
C10—O2—C9—C2	177.3 (2)	C1—C4—C5—C6	−0.1 (3)
C9—O2—C10—C11	−176.3 (2)	C1—C4—C5—C8	178.6 (2)
C13—O3—C12—O4	−0.1 (3)	C3—C4—C5—C6	−179.8 (3)
C13—O3—C12—C6	179.74 (19)	C3—C4—C5—C8	−1.0 (4)
C12—O3—C13—C14	−172.8 (2)	C4—C5—C6—S1	0.3 (3)
S1—C1—C4—C3	179.62 (17)	C4—C5—C6—C12	−179.2 (2)
S1—C1—C4—C5	−0.1 (3)	C8—C5—C6—S1	−178.41 (19)
S2—C1—C4—C3	0.1 (3)	C8—C5—C6—C12	2.1 (4)
S2—C1—C4—C5	−179.66 (17)	S1—C6—C12—O3	176.14 (16)
S2—C2—C3—C4	0.7 (3)	S1—C6—C12—O4	−4.0 (3)
S2—C2—C3—C7	−177.17 (19)	C5—C6—C12—O3	−4.4 (4)
C9—C2—C3—C4	−179.9 (2)	C5—C6—C12—O4	175.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O1	0.98	2.22	2.980 (3)	133
C8—H8A···O3	0.98	2.23	2.909 (3)	125
C11—H11A···O4i	0.98	2.53	3.471 (3)	161
C8—H8C···Cg2ii	0.98	2.74	3.578 (3)	144

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the S2/C1–C4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O1	0.98	2.22	2.980 (3)	133
C8—H8A⋯O3	0.98	2.23	2.909 (3)	125
C11—H11A⋯O4i	0.98	2.53	3.471 (3)	161
C8—H8C⋯Cg2ii	0.98	2.74	3.578 (3)	144

Symmetry codes: (i) ; (ii) .