1,4-Bis(thio­phen-2-yl)butane-1,4-dione

Guo, W.-T.; Miao, Z.-M.; Wang, Y.-L.

doi:10.1107/S1600536812005338

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o689-o690

doi:10.1107/S1600536812005338

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1,4-Bis(thiophen-2-yl)butane-1,4-dione

Wei-Ting Guo,^a Zhi-Min Miao ^a ^* and Yun-Long Wang ^a ^*

^aGout Laboratory, The Affiliated Hospital of Medical College Qingdao University, 16 Jiangsu Road, Qingdao, Shandong 266003, People's Republic of China
^*Correspondence e-mail: miao_zhimin@126.com, wangyunlongqd@163.com

(Received 23 January 2012; accepted 7 February 2012; online 10 February 2012)

In the centrosymmetric title compound, C₁₂H₁₀O₂S₂, the alkyl chains adopt a fully extended all-trans conformation with respect to the C(thiophene)—C bond. The non-H atoms of the molecule are nearly planar, with a maximum deviation of 0.063 (2) Å from the mean plane of the constituent atoms. In the crystal, symmetry-related molecules are linked via pairs of C—H⋯π contacts [H–centroid distances of the thiophene units = 2.79 (9) and 2.82 (4) Å], in turn interdigitating with each other along the bc plane, thus leading to an interwoven two-dimensional network.

Related literature

For related structures, see: Becerra et al. (2010 ); Liu et al. (2008 ); Nair, Devipriya & Eringathodi (2007 ); Nair, Vellalath et al. (2007 ); Bushueva et al. (2010 ). For background information on applications, see: Atalar et al. (2009 ); Chen et al. (2009 ); Charati et al. (2008 ); Cao et al. (2008 ); Wu et al. (2008 ). For the synthetic procedure, see: Schweiger et al. (2000 ). For bond lengths, see: Allen et al. (1987 ). For related C—H⋯π hydrogen bonds, see: Hu et al. (2008 ); Ishihara et al. (2007 ); Jennings et al. (2001 ).

Experimental

Crystal data

C₁₂H₁₀O₂S₂
M_r = 250.34
Monoclinic, P 2₁ /n
a = 5.6345 (3) Å
b = 6.2244 (3) Å
c = 16.3779 (9) Å
β = 92.902 (4)°
V = 573.66 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.957, T_max = 0.978
2000 measured reflections
1023 independent reflections
838 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.200
S = 1.09
1023 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C4/S1 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cg1ⁱ	0.93	2.79 (9)	3.610 (5)	146
C6—H6B⋯Cg1ⁱⁱ	0.97	2.82 (4)	3.637 (4)	143
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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/S1600536812005338/zj2057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005338/zj2057Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005338/zj2057Isup3.cml

checkCIF report

Comment top

Electroactive and photoactive thiophene-based molecules, oligomers, and polymers (Atalar et al., 2009; Chen et al., 2009; Charati et al., 2008; Becerra et al., 2010; Liu et al., 2008; Nair, Devipriya & Eringathodi, 2007; Nair, Vellalath et al., 2007; Bushueva et al.; 2010) are important for advanced technological applications, including display technologies, field-effect transistors, solar cells, sensors, nonlinear optics, molecular wires, and diodes (Cao et al., 2008; Wu et al., 2008). Thiophenes and its derivatives are originally applied to synthesize thiophene-based compounds, such as, oligomers and polythiophenes due to easy electropolymerization of thiophenes to produce stable, electrically conductive polymeric films. Thiophenes and its derivatives can also be widely used as building blocks in many agrochemicals and pharmaceuticals. To investigate the relationship between structure and pharmacological activity, the title compound was synthesized and its structure was determined by X-ray diffraction. As shown in figure 1, the centrosymmetric title compound lies across a crystallographic inversion centre which is situated at the midpoint of the C6–C6A (1.512 (8) Å, symmetry code: (A) 2-x, 1-y, 1-z) bond. The alkyl chains attached thiophenes adopt a fully extended all-trans conformation with respect to the C_thiophene–C bond. The non-H atoms of the molecule is nearly planar with O1 and O1A maximum deviation of 0.063 (2) Å from the mean plane of its constituting atoms. The C1–S1 and C4–S1 bond length of 1.678 (5) and 1.697 (4) Å, respectively, correspond to typical single C–S bonds. Whereas the C1–O1 (1.215 (5) Å) bond length indicate the presence of a typical double C═O bond (Allen et al., 1987). It is well-established that weak bonding interactions between entities, such as hydrogen-bonding and π-stacking, are important supramolecular forces, which can be used to govern the process of molecular recognition and selfassembly (Hu et al., 2008; Ishihara et al., 2007; Jennings et al., 2001). In the crystal structure, it is noteworthy that symmetry-related molecules, in turn, are linked via pairs of intermolecular C—H···π constacts [H–centroid distance of the thiophene units = 2.79 (9) - 2.82 (4) Å], and interdigitated with each other along bc plane, thus leading to an interwoven two dimensional network.

Related literature top

For related structures, see: Becerra et al. (2010); Liu et al. (2008); Nair, Devipriya & Eringathodi (2007); Nair, Vellalath et al. (2007); Bushueva et al. (2010). For background information on applications, see: Atalar et al. (2009); Chen et al. (2009); Charati et al. (2008); Cao et al. (2008); Wu et al. (2008). For the synthetic procedure, see: Schweiger et al. (2000). For bond lengths, see: Allen et al. (1987). For related C—H···π hydrogen bonds, see: Hu et al. (2008); Ishihara et al. (2007); Jennings et al. (2001).

Experimental top

Reagents and solvents were of commercially available quality. The title compound was synthesized according to the method of Schweiger et al. 2000. To a suspension of AlCl₃ (16 g, 0.12 mol) in CH₂Cl₂ (15 ml) a solution of thiophene (10 ml, 0.12 mol) and succinyl chloride (6 ml, 0.05 mol) in CH₂Cl₂ was added dropwise. The red mixture was stirred at r.t. for 18 h. This was then quenched with ice and conc. HCl (5 ml). After intensive stirring for 2 h the dark green organic phase was separated, washed with 2 M HCl, H₂O NaHCO₃ solution and dried over MgSO₄. After evaporation of the solvent a blue-green solid remained, which was suspended in ethanol. Filtration and washing with ethanol and diethyl ether provided a green solid. Column chromatography (SiO₂, CH₂Cl₂-hexane (1 : 1)) obtains (I) as a white solid 6.74 g (26.87 mmol; 54%). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the crude (5 g) in a mixture of water/ethanol (20 ml, 1:1, v/v) at room temperature.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, with displacement ellipsoids at the 30% probability level (Symmetry code: (A) 2-x, 1-y, 1-z).
	Fig. 2. The C–H···π stacking interactions (dashed lines) in the structure of the title compound viewing along bc plane, H atoms have been omitted for clarity, except for those involved in C–H···π stacking interactions.

1,4-Bis(thiophen-2-yl)butane-1,4-dione top

Crystal data top

C₁₂H₁₀O₂S₂	F(000) = 260
M_r = 250.34	D_x = 1.449 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1252 reflections
a = 5.6345 (3) Å	θ = 2.6–22.6°
b = 6.2244 (3) Å	µ = 0.44 mm⁻¹
c = 16.3779 (9) Å	T = 296 K
β = 92.902 (4)°	Bolck, yellow
V = 573.66 (5) Å³	0.20 × 0.15 × 0.10 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1023 independent reflections
Radiation source: fine-focus sealed tube	838 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.1°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→6
T_min = 0.957, T_max = 0.978	k = −7→6
2000 measured reflections	l = −19→19

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.200	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.105P)² + 0.7893P] where P = (F_o² + 2F_c²)/3
1023 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₂H₁₀O₂S₂	V = 573.66 (5) Å³
M_r = 250.34	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.6345 (3) Å	µ = 0.44 mm⁻¹
b = 6.2244 (3) Å	T = 296 K
c = 16.3779 (9) Å	0.20 × 0.15 × 0.10 mm
β = 92.902 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1023 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	838 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.978	R_int = 0.021
2000 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.200	H-atom parameters constrained
S = 1.09	Δρ_max = 0.58 e Å⁻³
1023 reflections	Δρ_min = −0.35 e Å⁻³
73 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.1013 (2)	−0.0356 (2)	0.69663 (7)	0.0577 (5)
C4	0.9593 (6)	0.0981 (6)	0.6181 (2)	0.0376 (9)
C5	1.0715 (7)	0.2877 (6)	0.5837 (2)	0.0403 (9)
C3	0.7295 (7)	0.0004 (6)	0.5931 (2)	0.0368 (9)
H3	0.6239	0.0483	0.5516	0.044*
C2	0.6983 (7)	−0.1823 (8)	0.6446 (3)	0.0537 (12)
H2	0.5649	−0.2702	0.6398	0.064*
C1	0.8824 (8)	−0.2171 (8)	0.7017 (3)	0.0515 (11)
H1	0.8850	−0.3295	0.7392	0.062*
O1	1.2671 (5)	0.3465 (5)	0.6091 (2)	0.0592 (9)
C6	0.9351 (7)	0.4030 (7)	0.5154 (2)	0.0419 (10)
H6A	0.7830	0.4485	0.5346	0.050*
H6B	0.9043	0.3038	0.4705	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0511 (8)	0.0646 (9)	0.0569 (8)	0.0067 (5)	−0.0020 (5)	0.0135 (6)
C4	0.0371 (19)	0.040 (2)	0.0356 (19)	0.0092 (16)	0.0000 (15)	−0.0042 (17)
C5	0.041 (2)	0.040 (2)	0.040 (2)	0.0079 (17)	0.0006 (16)	−0.0056 (17)
C3	0.039 (2)	0.038 (2)	0.0348 (19)	0.0114 (16)	0.0097 (15)	0.0031 (16)
C2	0.042 (2)	0.058 (3)	0.062 (3)	−0.002 (2)	0.012 (2)	−0.005 (2)
C1	0.047 (2)	0.054 (3)	0.055 (2)	0.008 (2)	0.0129 (19)	0.016 (2)
O1	0.0523 (18)	0.057 (2)	0.067 (2)	−0.0076 (15)	−0.0175 (15)	0.0107 (17)
C6	0.045 (2)	0.039 (2)	0.041 (2)	0.0047 (18)	−0.0052 (16)	−0.0003 (18)

Geometric parameters (Å, º) top

S1—C1	1.678 (5)	C3—H3	0.9300
S1—C4	1.697 (4)	C2—C1	1.379 (6)
C4—C5	1.466 (6)	C2—H2	0.9300
C4—C3	1.470 (6)	C1—H1	0.9300
C5—O1	1.215 (5)	C6—C6ⁱ	1.512 (8)
C5—C6	1.506 (5)	C6—H6A	0.9700
C3—C2	1.431 (6)	C6—H6B	0.9700

C1—S1—C4	92.8 (2)	C1—C2—H2	122.8
C5—C4—C3	128.1 (3)	C3—C2—H2	122.8
C5—C4—S1	119.4 (3)	C2—C1—S1	112.9 (3)
C3—C4—S1	112.5 (3)	C2—C1—H1	123.5
O1—C5—C4	120.8 (4)	S1—C1—H1	123.5
O1—C5—C6	122.1 (4)	C5—C6—C6ⁱ	113.0 (4)
C4—C5—C6	117.1 (3)	C5—C6—H6A	109.0
C2—C3—C4	107.3 (3)	C6ⁱ—C6—H6A	109.0
C2—C3—H3	126.4	C5—C6—H6B	109.0
C4—C3—H3	126.4	C6ⁱ—C6—H6B	109.0
C1—C2—C3	114.5 (4)	H6A—C6—H6B	107.8

C1—S1—C4—C5	−179.8 (3)	S1—C4—C3—C2	−0.1 (4)
C1—S1—C4—C3	−0.1 (3)	C4—C3—C2—C1	0.3 (5)
C3—C4—C5—O1	−177.6 (4)	C3—C2—C1—S1	−0.3 (5)
S1—C4—C5—O1	2.0 (5)	C4—S1—C1—C2	0.2 (4)
C3—C4—C5—C6	1.7 (6)	O1—C5—C6—C6ⁱ	−1.1 (7)
S1—C4—C5—C6	−178.6 (3)	C4—C5—C6—C6ⁱ	179.6 (4)
C5—C4—C3—C2	179.6 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C4/S1 or C1A–C4A/S1A ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cg1ⁱⁱ	0.93	2.79 (9)	3.610 (5)	146
C6—H6B···Cg1ⁱⁱⁱ	0.97	2.82 (4)	3.637 (4)	143

Symmetry codes: (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀O₂S₂
M_r	250.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.6345 (3), 6.2244 (3), 16.3779 (9)
β (°)	92.902 (4)
V (Å³)	573.66 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.957, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	2000, 1023, 838
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.200, 1.09
No. of reflections	1023
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.35

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C4/S1 or C1A–C4A/S1A ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cg1ⁱ	0.93	2.79 (9)	3.610 (5)	146
C6—H6B···Cg1ⁱⁱ	0.97	2.82 (4)	3.637 (4)	143

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+2, −y, −z+1.

Acknowledgements

The authors would like to thank the Gout Laboratory, The Affiliated Hospital of Medical College Qingdao University, for financial support.

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