Dimethyl 2,5-bis­(5-hexyl­thio­phen-2-yl)benzene-1,4-dioate

Song, C.-L.; Liu, K.; Zhang, A.-J.; Xu, Z.-G.; Zhang, H.-L.

doi:10.1107/S1600536811011718

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1059

doi:10.1107/S1600536811011718

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Dimethyl 2,5-bis(5-hexylthiophen-2-yl)benzene-1,4-dioate

Cheng-Li Song,^a Ke Liu,^a Ai-Jiang Zhang,^a Zhu-Guo Xu ^a ^* and Hao-Li Zhang ^a

^aState Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, People's Republic of China
^*Correspondence e-mail: xuzhg@lzu.edu.cn

(Received 26 March 2011; accepted 29 March 2011; online 7 April 2011)

In the title compound, C₃₀H₃₈O₄S₂, the centroid of the benzene ring lies on a center of inversion. The thiophene ring is aligned at 49.8 (1)° with respect to the benzene ring. The alkyl chain adopts an extended zigzag conformation.

Related literature

The title compound and its derivatives are used in the preparation of organic semiconductors. For applications of these materials, see: Tian et al. (2010 ); Zhang et al. (2010 ). For the synthesis of related compounds, see: Fraind & Tovar (2010 ); Gurthrie & Tovar (2008 ), Hotta (2001 ); Kang et al. (1997 ); Lois et al. (2007 ); Shao & Zhao (2009 ); Zhao et al. (2007 ).

Experimental

Crystal data

C₃₀H₃₈O₄S₂
M_r = 526.72
Monoclinic, P 2/c
a = 15.617 (6) Å
b = 8.083 (3) Å
c = 11.585 (4) Å
β = 104.470 (4)°
V = 1416.0 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.35 × 0.32 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.927, T_max = 0.959
6083 measured reflections
2490 independent reflections
1865 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.104
S = 1.04
2490 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011718/ng5141sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011718/ng5141Isup2.hkl

checkCIF report

Comment top

The title compound and its derivatives are important materials for the preparation of various organic semiconductors, which could find applications in the fields of organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) or solar cells (Tian et al., 2010; Zhang et al., 2010). The device performance of these organic semiconductors are strongly dependent on the molecular packing in their crystals. This led us to pay attention to the synthesis and crystal structure of the compound. Herein, we report the synthesis and structure of the title compound, namely dimethyl 2,5-bis(5-hexylthiophen-2-yl)benzene-1,4-dioate.

The molecular structure of the title compound is shown in Fig.1. Bond lengths and angles in the molecule are within normal ranges. The bond length of C—H in the thiophene and the benzene rings is 0.93 Å and the angle formed by C—S—C in the thiophene is 92.79°. In this structure, the two thiophene rings and the benzene ring are not in the same plane, which give a dihedral angle of 49.84°.

Related literature top

The title compound and its derivatives are used in the preparation of organic semiconductors. For applications of these materials, see: Tian et al. (2010); Zhang et al. (2010). For the synthesis of related compounds, see: Fraind & Tovar (2010); Gurthrie & Tovar (2008), Hotta (2001); Kang et al. (1997); Lois et al. (2007); Shao & Zhao (2009); Zhao et al. (2007).

Experimental top

The title compound was synthesized by Suzuki cross-coupling reaction. Briefly, thiophene-2-boronic acid (2.52 g, 10.00 mmol), dimethyl 2,5-dibromobenzene-1,4-dioate (880 mg, 2.50 mmol), Pd(PPh₃)₄ (115 mg, 0.10 mmol) and NaHCO₃ (840 mg, 10.00 mmol) were mixed in dry THF (10 ml) under argon. The mixture was stirred and refluxed for 24 hrs (monitored by TLC) to give the title compound. The product was purified by column chromatography. Colorless crystals were grown via evaporation from n-hexane and dichloromethane (10:1, v:v) mixture solvents at room temperature for X-ray diffraction.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Symmetry operations: a = -x, 1 - y, -z.
	Fig. 2. Molecular packing of the title compound (I).

Dimethyl 2,5-bis(5-hexylthiophen-2-yl)benzene-1,4-dioate top

Crystal data top

C₃₀H₃₈O₄S₂	F(000) = 564
M_r = 526.72	D_x = 1.235 Mg m⁻³
Monoclinic, P2/c	Melting point: 362 K
Hall symbol: -P 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 15.617 (6) Å	Cell parameters from 1616 reflections
b = 8.083 (3) Å	θ = 2.5–25.8°
c = 11.585 (4) Å	µ = 0.22 mm⁻¹
β = 104.470 (4)°	T = 293 K
V = 1416.0 (9) Å³	Block, colorless
Z = 2	0.35 × 0.32 × 0.19 mm

Data collection top

Bruker APEXII CCD diffractometer	2490 independent reflections
Radiation source: fine-focus sealed tube	1865 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −16→18
T_min = 0.927, T_max = 0.959	k = −8→9
6083 measured reflections	l = −13→13

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0496P)² + 0.1877P] where P = (F_o² + 2F_c²)/3
2490 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₃₀H₃₈O₄S₂	V = 1416.0 (9) Å³
M_r = 526.72	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 15.617 (6) Å	µ = 0.22 mm⁻¹
b = 8.083 (3) Å	T = 293 K
c = 11.585 (4) Å	0.35 × 0.32 × 0.19 mm
β = 104.470 (4)°

Data collection top

Bruker APEXII CCD diffractometer	2490 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1865 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.959	R_int = 0.031
6083 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.04	Δρ_max = 0.16 e Å⁻³
2490 reflections	Δρ_min = −0.23 e Å⁻³
165 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.07441 (12)	0.8250 (2)	−0.01209 (17)	0.0320 (5)
C2	0.03976 (12)	0.6534 (2)	−0.00661 (17)	0.0301 (4)
C3	0.07574 (12)	0.5472 (2)	0.08892 (16)	0.0309 (5)
C4	0.15632 (12)	0.5867 (2)	0.18357 (17)	0.0329 (5)
C5	0.16918 (13)	0.5716 (3)	0.30285 (18)	0.0411 (5)
H5	0.1254	0.5364	0.3388	0.049*
C6	0.25579 (14)	0.6143 (3)	0.36780 (19)	0.0457 (6)
H6	0.2739	0.6121	0.4506	0.055*
C7	0.30953 (12)	0.6585 (2)	0.29820 (18)	0.0364 (5)
C8	0.40559 (13)	0.7071 (3)	0.3327 (2)	0.0480 (6)
H8A	0.4122	0.8115	0.2946	0.058*
H8B	0.4393	0.6246	0.3020	0.058*
C9	0.44453 (13)	0.7245 (3)	0.4653 (2)	0.0472 (6)
H9A	0.4376	0.6205	0.5037	0.057*
H9B	0.4115	0.8080	0.4960	0.057*
C10	0.54203 (14)	0.7720 (3)	0.4984 (2)	0.0504 (6)
H10A	0.5750	0.6890	0.4672	0.060*
H10B	0.5489	0.8764	0.4604	0.060*
C11	0.58113 (14)	0.7884 (3)	0.6310 (2)	0.0539 (6)
H11A	0.5466	0.8688	0.6621	0.065*
H11B	0.5752	0.6830	0.6682	0.065*
C12	0.67691 (15)	0.8399 (3)	0.6673 (2)	0.0581 (7)
H12A	0.7115	0.7618	0.6342	0.070*
H12B	0.6827	0.9475	0.6330	0.070*
C13	0.71464 (18)	0.8491 (3)	0.7999 (2)	0.0792 (9)
H13A	0.6816	0.9277	0.8334	0.119*
H13B	0.7754	0.8833	0.8164	0.119*
H13C	0.7111	0.7422	0.8345	0.119*
C14	0.03448 (12)	0.3957 (2)	0.09348 (17)	0.0327 (5)
H14	0.0574	0.3248	0.1569	0.039*
C15	0.11166 (16)	1.0295 (3)	−0.1356 (2)	0.0549 (6)
H15A	0.0682	1.1060	−0.1218	0.082*
H15B	0.1181	1.0434	−0.2153	0.082*
H15C	0.1673	1.0503	−0.0797	0.082*
O1	0.08339 (9)	0.86154 (16)	−0.12051 (12)	0.0441 (4)
O2	0.09033 (9)	0.91985 (17)	0.07033 (12)	0.0444 (4)
S1	0.25288 (3)	0.65154 (7)	0.15037 (5)	0.0447 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0258 (10)	0.0378 (11)	0.0301 (12)	−0.0019 (8)	0.0026 (9)	−0.0002 (9)
C2	0.0278 (10)	0.0345 (10)	0.0280 (11)	−0.0041 (8)	0.0071 (8)	−0.0029 (9)
C3	0.0264 (10)	0.0364 (11)	0.0283 (12)	−0.0025 (8)	0.0039 (8)	−0.0035 (9)
C4	0.0285 (10)	0.0340 (10)	0.0337 (12)	−0.0047 (8)	0.0031 (9)	−0.0004 (9)
C5	0.0347 (12)	0.0546 (13)	0.0321 (13)	−0.0116 (10)	0.0048 (9)	0.0031 (10)
C6	0.0422 (13)	0.0577 (14)	0.0311 (13)	−0.0109 (10)	−0.0025 (10)	0.0009 (10)
C7	0.0282 (10)	0.0383 (11)	0.0379 (13)	−0.0035 (9)	−0.0010 (9)	−0.0023 (9)
C8	0.0298 (11)	0.0531 (13)	0.0562 (16)	−0.0086 (10)	0.0017 (11)	−0.0064 (11)
C9	0.0319 (12)	0.0486 (13)	0.0535 (15)	−0.0053 (10)	−0.0032 (11)	−0.0030 (11)
C10	0.0336 (12)	0.0491 (13)	0.0603 (17)	−0.0045 (10)	−0.0037 (11)	−0.0043 (12)
C11	0.0404 (13)	0.0528 (14)	0.0580 (17)	−0.0087 (11)	−0.0072 (12)	0.0015 (12)
C12	0.0387 (13)	0.0582 (15)	0.0659 (18)	−0.0052 (11)	−0.0086 (12)	−0.0039 (13)
C13	0.0651 (18)	0.085 (2)	0.066 (2)	−0.0177 (15)	−0.0225 (15)	0.0089 (16)
C14	0.0298 (10)	0.0379 (11)	0.0279 (11)	−0.0003 (8)	0.0023 (9)	0.0011 (9)
C15	0.0672 (16)	0.0483 (14)	0.0546 (16)	−0.0134 (12)	0.0257 (13)	0.0083 (11)
O1	0.0577 (10)	0.0423 (9)	0.0349 (9)	−0.0128 (7)	0.0162 (7)	−0.0015 (6)
O2	0.0542 (9)	0.0409 (8)	0.0345 (9)	−0.0097 (7)	0.0039 (7)	−0.0071 (7)
S1	0.0315 (3)	0.0660 (4)	0.0355 (4)	−0.0110 (3)	0.0062 (2)	−0.0034 (3)

Geometric parameters (Å, º) top

C1—O2	1.201 (2)	C9—H9B	0.9700
C1—O1	1.331 (2)	C10—C11	1.510 (3)
C1—C2	1.496 (3)	C10—H10A	0.9700
C2—C14ⁱ	1.390 (3)	C10—H10B	0.9700
C2—C3	1.403 (3)	C11—C12	1.508 (3)
C3—C14	1.391 (3)	C11—H11A	0.9700
C3—C4	1.483 (2)	C11—H11B	0.9700
C4—C5	1.351 (3)	C12—C13	1.503 (3)
C4—S1	1.728 (2)	C12—H12A	0.9700
C5—C6	1.416 (3)	C12—H12B	0.9700
C5—H5	0.9300	C13—H13A	0.9600
C6—C7	1.349 (3)	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—C8	1.505 (3)	C14—C2ⁱ	1.390 (3)
C7—S1	1.721 (2)	C14—H14	0.9300
C8—C9	1.511 (3)	C15—O1	1.452 (2)
C8—H8A	0.9700	C15—H15A	0.9600
C8—H8B	0.9700	C15—H15B	0.9600
C9—C10	1.523 (3)	C15—H15C	0.9600
C9—H9A	0.9700

O2—C1—O1	123.96 (18)	C11—C10—H10A	108.8
O2—C1—C2	124.28 (18)	C9—C10—H10A	108.8
O1—C1—C2	111.74 (16)	C11—C10—H10B	108.8
C14ⁱ—C2—C3	119.57 (16)	C9—C10—H10B	108.8
C14ⁱ—C2—C1	118.65 (16)	H10A—C10—H10B	107.7
C3—C2—C1	121.56 (16)	C12—C11—C10	115.4 (2)
C14—C3—C2	118.10 (17)	C12—C11—H11A	108.4
C14—C3—C4	118.50 (17)	C10—C11—H11A	108.4
C2—C3—C4	123.39 (17)	C12—C11—H11B	108.4
C5—C4—C3	128.22 (18)	C10—C11—H11B	108.4
C5—C4—S1	109.88 (14)	H11A—C11—H11B	107.5
C3—C4—S1	121.82 (14)	C13—C12—C11	114.0 (2)
C4—C5—C6	113.54 (19)	C13—C12—H12A	108.7
C4—C5—H5	123.2	C11—C12—H12A	108.7
C6—C5—H5	123.2	C13—C12—H12B	108.7
C7—C6—C5	113.65 (19)	C11—C12—H12B	108.7
C7—C6—H6	123.2	H12A—C12—H12B	107.6
C5—C6—H6	123.2	C12—C13—H13A	109.5
C6—C7—C8	129.7 (2)	C12—C13—H13B	109.5
C6—C7—S1	110.14 (15)	H13A—C13—H13B	109.5
C8—C7—S1	120.20 (16)	C12—C13—H13C	109.5
C7—C8—C9	114.55 (19)	H13A—C13—H13C	109.5
C7—C8—H8A	108.6	H13B—C13—H13C	109.5
C9—C8—H8A	108.6	C2ⁱ—C14—C3	122.33 (18)
C7—C8—H8B	108.6	C2ⁱ—C14—H14	118.8
C9—C8—H8B	108.6	C3—C14—H14	118.8
H8A—C8—H8B	107.6	O1—C15—H15A	109.5
C8—C9—C10	113.74 (19)	O1—C15—H15B	109.5
C8—C9—H9A	108.8	H15A—C15—H15B	109.5
C10—C9—H9A	108.8	O1—C15—H15C	109.5
C8—C9—H9B	108.8	H15A—C15—H15C	109.5
C10—C9—H9B	108.8	H15B—C15—H15C	109.5
H9A—C9—H9B	107.7	C1—O1—C15	115.35 (16)
C11—C10—C9	113.8 (2)	C7—S1—C4	92.78 (10)

O2—C1—C2—C14ⁱ	129.1 (2)	C5—C6—C7—S1	1.1 (2)
O1—C1—C2—C14ⁱ	−49.3 (2)	C6—C7—C8—C9	−6.6 (3)
O2—C1—C2—C3	−45.5 (3)	S1—C7—C8—C9	174.20 (15)
O1—C1—C2—C3	136.11 (18)	C7—C8—C9—C10	179.42 (19)
C14ⁱ—C2—C3—C14	−0.7 (3)	C8—C9—C10—C11	−179.62 (19)
C1—C2—C3—C14	173.85 (17)	C9—C10—C11—C12	−178.4 (2)
C14ⁱ—C2—C3—C4	178.01 (17)	C10—C11—C12—C13	−177.9 (2)
C1—C2—C3—C4	−7.4 (3)	C2—C3—C14—C2ⁱ	0.7 (3)
C14—C3—C4—C5	−48.0 (3)	C4—C3—C14—C2ⁱ	−178.05 (17)
C2—C3—C4—C5	133.3 (2)	O2—C1—O1—C15	−2.0 (3)
C14—C3—C4—S1	128.25 (17)	C2—C1—O1—C15	176.42 (16)
C2—C3—C4—S1	−50.5 (2)	C6—C7—S1—C4	−0.48 (17)
C3—C4—C5—C6	177.57 (18)	C8—C7—S1—C4	178.84 (17)
S1—C4—C5—C6	0.9 (2)	C5—C4—S1—C7	−0.28 (16)
C4—C5—C6—C7	−1.4 (3)	C3—C4—S1—C7	−177.16 (16)
C5—C6—C7—C8	−178.1 (2)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₃₀H₃₈O₄S₂
M_r	526.72
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	293
a, b, c (Å)	15.617 (6), 8.083 (3), 11.585 (4)
β (°)	104.470 (4)
V (Å³)	1416.0 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.35 × 0.32 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.927, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	6083, 2490, 1865
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.104, 1.04
No. of reflections	2490
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.23

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors are grateful for financial support from the National Natural Science Foundation of China (NSFC; 20872055, 21073079, J0730425) and the 111 project.

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