1,4-Bis(1H-benzimidazol-2-yl)benzene methanol monosolvate

Jiang-Bo Su; Shen Lin; Li-Juan Chen; Ming-Xing Yang; Hua Huang

doi:10.1107/S1600536810049238

. 2010 Dec 11;67(Pt 1):o90. doi: 10.1107/S1600536810049238

1,4-Bis(1H-benzimidazol-2-yl)benzene methanol monosolvate

Jiang-Bo Su ^a, Shen Lin ^a,^*, Li-Juan Chen ^a, Ming-Xing Yang ^a, Hua Huang ^a

PMCID: PMC3050263 PMID: 21522799

Abstract

The asymmetric unit of the title compound, C₂₀H₁₄N₄·CH₄O, contains two independent half-molecules, each located on an inversion centre, and a methanol solvent molecule. The benzimidazolyl groups form different dihedral angles [24.0 (1) and 11.6 (1)°] with the plane of the central benzene ring in the two molecules. In the crystal, a two-dimensional network is formed through N—H⋯ N, N—H⋯O and O—H⋯N hydrogen-bonding interactions between the benzimidazole units and methanol solvent molecules. π–π stacking interactions also occur between the benzimidazole rings of adjacent molecules, with centroid–centroid distances of 3.720 (14) Å and interplanar distances of 3.53 (1) Å .

Related literature

For the synthesis of the title compound see: Wu et al. (2009 ▶). For the properties and applications of benzimidazoles, see: Tidwell et al. (1993 ▶); Salunke et al. (1994 ▶); Hoorn et al. (1995 ▶); van Berkel et al. (1995 ▶); Dinolfo et al. (2005 ▶); Yang et al. (2008 ▶). For structures of 1,4-bis(benzimidazol-2-yl)benzene analogues, see: Bei et al. (2000 ▶); Wu et al. (2009 ▶). For bond lengths and angles in similar structures, see: Matthews et al. (1996 ▶); Ozbey et al. (1998 ▶).

Experimental

Crystal data

C₂₀H₁₄N₄·CH₄O
M _r = 342.39
Triclinic,
a = 7.1730 (14) Å
b = 10.599 (2) Å
c = 12.260 (3) Å
α = 76.21 (3)°
β = 88.37 (3)°
γ = 77.01 (3)°
V = 881.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.31 × 0.16 × 0.12 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002 ▶) T _min = 0.432, T _max = 1.000
4565 measured reflections
3139 independent reflections
2577 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.119
S = 1.04
3139 reflections
240 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrystalClear (Rigaku, 2002 ▶); 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/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049238/bg2370sup1.cif

e-67-00o90-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049238/bg2370Isup2.hkl

e-67-00o90-Isup2.hkl^{(154KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.93 (3)	1.93 (3)	2.829 (2)	162 (2)
N2—H2A⋯N3	0.86	2.03	2.873 (2)	168
N4—H4A⋯O1ⁱ	0.86	1.99	2.855 (2)	179

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 20771024), the Natural Science Foundation of Fujian Province (No. 2008 J0142) and the Key Project Fund of Science and Technology of Fujian Province (No. 2008I0013).

supplementary crystallographic information

Comment

In earlier communications (Tidwell, et al., 1993; Salunke, et al., 1994; Hoorn, et al., 1995; van Berkel, et al., 1995; Dinolfo et al., 2005; Yang et al., 2008;) it has been reported that the benzimidazole moiety is an important heterocyclic ring not only because of its wide-ranging antivirus activity, its importance in selective ion-exchange resin, but also because of the interest in the coordination chemistry of azoles acting as ligands in transition metal compounds. However, the crystal structure of 1,4-bis(benzimidazol-2-yl)benzene analogues have rarely been reported (Bei, et al., 2000; Wu, et al., 2009;). Herein, we report the crystal structure of the title compound, 1,4-bis(benzimidazol-2-yl)benzene methanol solvate (1).

The structure of title compound is illustrated in Fig. 1. The asymmetric unit contains two different molecules halved by inversion centres at (1/2, 1/2, 1/2) and (0, 1, 0), respectively, and a methanol solvent. Bond lengths and angles have normal values and are comparable to those reported in similar structures (Matthews et al., 1996; Ozbey et al., 1998). The benzimidazoyl moieties form different dihedral angles with the plane of the central benzene ring (24.0 (1)°, 11.6 (1)° for A and B, respectively, Fig. 1). C—N bond lengths in the imidazole ring are in the range 1.328 (2)–1.391 (2) Å, shorter than typical single C—N bond lengths (ca 1.48 Å) and longer than typical C=N ones (ca 1.28 Å), indicating partial double-bond character. This can be interpreted in terms of conjugation in the heterocycle(Fig. 1, Table 1).

In the solid state the 1,4-bis(Benzimidazol-2-yl)benzene moieties are connected to form a two-dimensional network through intermolecular N—H··· N, N—H···O and O—H···N hydrogen bonds (Fig.2, Table 2). Moreover, there exists π-π stacking interactions between the aromatic and imidazole rings of adjacent molecules, with intercentroid/interplanar distances of about 3.72 (1) Å /3.53 (1) Å, respectively.

Experimental

All reagents were of AR grade available commercially and used without further purification. To a mixed solvent of polyphosphoric acid (5 ml) and Phosphoric acid (15 ml, 85%) was added benzene-1,4-dicarboxylic acid (1.67 g, 10.0 mmol) and 1,2-diaminobenzene (2.16 g, 20.0 mmol). The mixture was heated slowly to 398 K, and the resulting solution was stirred at 453 K for five hours, and was poured into 300 ml water. Then the mixture was neutralized with 50% sodium hydroxide solution. The crude product was collected by filtration, dried and recrystallized (yield 67%). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a methanol solution.