(E)-2-[2-(2-Thien­yl)vin­yl]-1H-1,3-benzimidazole

Hang, T.; Ye, Q.

doi:10.1107/S1600536808006405

organic compounds

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Volume 64| Part 6| June 2008| Page o964

doi:10.1107/S1600536808006405

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(E)-2-[2-(2-Thienyl)vinyl]-1H-1,3-benzimidazole

Tian Hang ^a and Qiong Ye ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: yeqiong@seu.edu.cn

(Received 27 January 2008; accepted 7 March 2008; online 3 May 2008)

In the title compound, C₁₃H₁₀N₂S, the dihedral angle between the imidazole and thiophene rings is 16.89 (19)°, and the double bond adopts an E configuration. In the crystal structure, N—H⋯N hydrogen bonds link the molecules into rows along b. There is also evidence of weak C—H⋯S interactions.

Related literature

For general background, see: Huang et al. (2003 ); Wang et al. (2005 ); Ye et al. (2006 , 2007 ). For the crystal structures of related compounds, see: Ozbey et al. (1998 ); Li & Clarkson (2007 ).

Experimental

Crystal data

C₁₃H₁₀N₂S
M_r = 226.06
Orthorhombic, P n n a
a = 12.239 (2) Å
b = 16.389 (3) Å
c = 11.487 (2) Å
V = 2304.1 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 (2) K
0.15 × 0.10 × 0.07 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.796, T_max = 1.000 (expected range = 0.782–0.983)
21849 measured reflections
2637 independent reflections
1360 reflections with I > 2σ(I)
R_int = 0.145

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.214
S = 1.07
2637 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯S1	0.93	2.76	3.161 (4)	107
N1—H1B⋯N1ⁱ	0.86	2.01	2.865 (6)	170
N2—H2B⋯N2ⁱⁱ	0.86	2.11	2.906 (5)	154
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y, z]$ ; (ii) $[x, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536808006405/sj2460sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006405/sj2460Isup2.hkl

checkCIF report

Comment top

It has been generally accepted that imidazole groups play an important role in coordination chemistry (Huang et al., 2003). A flexible ligand readily induces coordination compounds to crystallize in non-centrosymmetric space groups, which makes it possible to investigate their interesting physical properties such as second harmonic generation, ferroelectric and piezoelectric properties (Wang et al., 2005). As a continuation of our work in this field, (Ye et al., 2006, 2007), we have synthesized the title compound, 1, Fig 1.

The title compound, C₁₂H₁₀N₂S, was successfully prepared through the reaction between 2-methyl-1H-benzo[d]imidazole and thiophene-2-carbaldehyde. It adopts a trans configuration about the C9?C11 bond and the dihedral angle between the mean plane of the imidazole ring and thiophenyl ring is 16.89 (19)°. The crystal packing is dominated by N—H···N interactions linking the molecules into rows along b, Fig 2. There is also evidence of weak C—H···S interactions.

Related literature top

For general background, see: Huang et al. (2003); Wang et al. (2005); Ye et al. (2006, 2007). For the crystal structures of related compounds, see: Ozbey et al. (1998); Li & Clarkson (2007).

Experimental top

2-methyl-1H-benzo[d]imidazole (10 mmol, 1.32 g) and thiophene-2-carbaldehyde (45 mmol, 5.04 g) were reacted as a melt at 180°C with stirring for 18 h. Then 20 ml 2-propanol and 1.5 g oxalic acid were added to the reaction mixture, the solution filtered and the precipitate washed with copious quantities of boiling water. The pH was adjusted to 8–9 with ammonia to afford the title compound as a pale-yellow solid powder. Crystals suitable for single-crystal X-ray diffraction studies were obtained by slow evaporation of a solution in ethanol at room temperature over several days.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 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 compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The crystal packing of 1 with hydrogen bonds drawn as dashed lines.

(E)-2-[2-(2-Thienyl)vinyl]-1H-1,3-benzimidazole top

Crystal data top

C₁₃H₁₀N₂S	F(000) = 944
M_r = 226.06	D_x = 1.305 Mg m⁻³
Orthorhombic, Pnna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bc	Cell parameters from 14820 reflections
a = 12.239 (2) Å	θ = 3.0–29.2°
b = 16.389 (3) Å	µ = 0.25 mm⁻¹
c = 11.487 (2) Å	T = 293 K
V = 2304.1 (7) Å³	Block, colorless
Z = 8	0.15 × 0.10 × 0.07 mm

Data collection top

Mercury2 (2x2 bin mode) diffractometer	2637 independent reflections
Radiation source: fine-focus sealed tube	1360 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.145
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
CCD profile fitting scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −21→21
T_min = 0.796, T_max = 1.000	l = −14→14
21849 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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.214	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.081P)² + 0.7151P] where P = (F_o² + 2F_c²)/3
2637 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₃H₁₀N₂S	V = 2304.1 (7) Å³
M_r = 226.06	Z = 8
Orthorhombic, Pnna	Mo Kα radiation
a = 12.239 (2) Å	µ = 0.25 mm⁻¹
b = 16.389 (3) Å	T = 293 K
c = 11.487 (2) Å	0.15 × 0.10 × 0.07 mm

Data collection top

Mercury2 (2x2 bin mode) diffractometer	2637 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1360 reflections with I > 2σ(I)
T_min = 0.796, T_max = 1.000	R_int = 0.145
21849 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	1 restraint
wR(F²) = 0.214	H-atom parameters constrained
S = 1.07	Δρ_max = 0.22 e Å⁻³
2637 reflections	Δρ_min = −0.28 e Å⁻³
145 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	Occ. (<1)
S1	0.88515 (10)	0.06908 (7)	0.51647 (11)	0.0801 (5)
N1	0.6821 (2)	0.07121 (18)	0.1000 (3)	0.0577 (9)
H1B	0.7264	0.0309	0.0924	0.069*	0.50
N2	0.5945 (2)	0.17665 (16)	0.1790 (2)	0.0452 (7)
H2B	0.5751	0.2134	0.2283	0.054*	0.50
C1	0.5111 (4)	0.1178 (3)	−0.1555 (4)	0.0824 (14)
H1A	0.4956	0.1028	−0.2319	0.099*
C2	0.8179 (4)	0.1317 (3)	0.7051 (4)	0.0898 (15)
H2A	0.8136	0.1453	0.7836	0.108*
C3	0.8987 (5)	0.0855 (3)	0.6610 (4)	0.0890 (16)
H3A	0.9559	0.0647	0.7053	0.107*
C4	0.7391 (3)	0.1583 (3)	0.6209 (3)	0.0653 (11)
H4A	0.6790	0.1913	0.6364	0.078*
C5	0.5901 (4)	0.0750 (3)	−0.0942 (4)	0.0753 (13)
H5A	0.6278	0.0316	−0.1277	0.090*
C6	0.4751 (3)	0.2076 (2)	0.0054 (3)	0.0604 (11)
H6A	0.4376	0.2514	0.0381	0.073*
C7	0.4546 (4)	0.1825 (3)	−0.1057 (4)	0.0720 (12)
H7A	0.4015	0.2094	−0.1492	0.086*
C8	0.7672 (3)	0.1264 (2)	0.5105 (3)	0.0581 (10)
C9	0.7079 (3)	0.1380 (2)	0.4039 (3)	0.0532 (10)
H9A	0.6461	0.1709	0.4074	0.064*
C10	0.6101 (3)	0.0995 (2)	0.0186 (3)	0.0515 (9)
C11	0.7328 (3)	0.1064 (2)	0.3007 (3)	0.0526 (10)
H11A	0.7950	0.0740	0.2961	0.063*
C12	0.6700 (3)	0.1188 (2)	0.1941 (3)	0.0479 (9)
C13	0.5538 (3)	0.1655 (2)	0.0678 (3)	0.0461 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0830 (9)	0.0654 (8)	0.0918 (10)	−0.0012 (6)	−0.0304 (7)	0.0032 (6)
N1	0.0607 (19)	0.0583 (19)	0.054 (2)	0.0158 (16)	−0.0072 (15)	−0.0140 (16)
N2	0.0532 (17)	0.0401 (16)	0.0422 (17)	0.0063 (13)	0.0015 (13)	−0.0027 (13)
C1	0.097 (3)	0.096 (4)	0.054 (3)	0.004 (3)	−0.017 (3)	−0.015 (3)
C2	0.113 (4)	0.106 (4)	0.050 (3)	−0.026 (3)	−0.023 (2)	0.013 (3)
C3	0.112 (4)	0.076 (3)	0.079 (4)	−0.023 (3)	−0.043 (3)	0.023 (3)
C4	0.070 (3)	0.081 (3)	0.045 (2)	−0.018 (2)	−0.0037 (18)	0.001 (2)
C5	0.083 (3)	0.079 (3)	0.064 (3)	0.018 (2)	−0.011 (2)	−0.028 (2)
C6	0.072 (3)	0.054 (2)	0.055 (2)	0.009 (2)	−0.009 (2)	0.001 (2)
C7	0.081 (3)	0.071 (3)	0.064 (3)	0.009 (2)	−0.021 (2)	0.007 (2)
C8	0.063 (2)	0.051 (2)	0.061 (3)	−0.0153 (19)	−0.014 (2)	0.0087 (19)
C9	0.055 (2)	0.049 (2)	0.056 (3)	−0.0009 (18)	−0.0023 (18)	0.0054 (18)
C10	0.053 (2)	0.051 (2)	0.051 (2)	0.0034 (18)	−0.0051 (18)	−0.0070 (18)
C11	0.051 (2)	0.048 (2)	0.059 (3)	0.0005 (17)	−0.0004 (19)	−0.0009 (18)
C12	0.048 (2)	0.049 (2)	0.047 (2)	−0.0011 (17)	0.0016 (17)	0.0022 (17)
C13	0.052 (2)	0.0418 (19)	0.044 (2)	−0.0023 (17)	0.0020 (17)	0.0001 (16)

Geometric parameters (Å, º) top

S1—C3	1.690 (5)	C4—C8	1.415 (5)
S1—C8	1.723 (4)	C4—H4A	0.9300
N1—C12	1.341 (4)	C5—C10	1.379 (5)
N1—C10	1.366 (4)	C5—H5A	0.9300
N1—H1B	0.8600	C6—C7	1.365 (5)
N2—C12	1.335 (4)	C6—C13	1.385 (5)
N2—C13	1.383 (4)	C6—H6A	0.9300
N2—H2B	0.8600	C7—H7A	0.9300
C1—C5	1.386 (6)	C8—C9	1.436 (5)
C1—C7	1.390 (6)	C9—C11	1.329 (5)
C1—H1A	0.9300	C9—H9A	0.9300
C2—C3	1.344 (6)	C10—C13	1.401 (5)
C2—C4	1.435 (6)	C11—C12	1.461 (4)
C2—H2A	0.9300	C11—H11A	0.9300
C3—H3A	0.9300

C3—S1—C8	92.0 (3)	C7—C6—H6A	121.3
C12—N1—C10	106.4 (3)	C13—C6—H6A	121.3
C12—N1—H1B	126.8	C6—C7—C1	121.6 (4)
C10—N1—H1B	126.8	C6—C7—H7A	119.2
C12—N2—C13	106.0 (3)	C1—C7—H7A	119.2
C12—N2—H2B	127.0	C4—C8—C9	126.3 (4)
C13—N2—H2B	127.0	C4—C8—S1	111.7 (3)
C5—C1—C7	121.6 (4)	C9—C8—S1	122.0 (3)
C5—C1—H1A	119.2	C11—C9—C8	126.3 (4)
C7—C1—H1A	119.2	C11—C9—H9A	116.8
C3—C2—C4	114.3 (4)	C8—C9—H9A	116.8
C3—C2—H2A	122.8	N1—C10—C5	131.2 (4)
C4—C2—H2A	122.8	N1—C10—C13	107.7 (3)
C2—C3—S1	112.8 (4)	C5—C10—C13	121.1 (4)
C2—C3—H3A	123.6	C9—C11—C12	125.0 (3)
S1—C3—H3A	123.6	C9—C11—H11A	117.5
C8—C4—C2	109.2 (4)	C12—C11—H11A	117.5
C8—C4—H4A	125.4	N1—C12—N2	112.7 (3)
C2—C4—H4A	125.4	N1—C12—C11	122.5 (3)
C1—C5—C10	117.0 (4)	N2—C12—C11	124.9 (3)
C1—C5—H5A	121.5	N2—C13—C6	131.5 (3)
C10—C5—H5A	121.5	N2—C13—C10	107.3 (3)
C7—C6—C13	117.5 (4)	C6—C13—C10	121.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···S1	0.93	2.76	3.161 (4)	107
N1—H1B···N1ⁱ	0.86	2.01	2.865 (6)	170
N2—H2B···N2ⁱⁱ	0.86	2.11	2.906 (5)	154

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀N₂S
M_r	226.06
Crystal system, space group	Orthorhombic, Pnna
Temperature (K)	293
a, b, c (Å)	12.239 (2), 16.389 (3), 11.487 (2)
V (Å³)	2304.1 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.15 × 0.10 × 0.07

Data collection
Diffractometer	Mercury2 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.796, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	21849, 2637, 1360
R_int	0.145
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.214, 1.07
No. of reflections	2637
No. of parameters	145
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···S1	0.93	2.76	3.161 (4)	106.9
N1—H1B···N1ⁱ	0.86	2.01	2.865 (6)	170.0
N2—H2B···N2ⁱⁱ	0.86	2.11	2.906 (5)	154.2

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

Acknowledgements

This work was supported by a Start-up Grant from Southeast University (to YQ).

References

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