2-[(1H-Benzimidazol-1-yl)meth­yl]phenol benzene hemisolvate

Augusto Rivera; Leonardo Jiménez-Cruz; Michael Bolte

doi:10.1107/S1600536814000841

. 2014 Jan 22;70(Pt 2):o177. doi: 10.1107/S1600536814000841

2-[(1H-Benzimidazol-1-yl)methyl]phenol benzene hemisolvate

Augusto Rivera ^a,^*, Leonardo Jiménez-Cruz ^a, Michael Bolte ^b

PMCID: PMC3998331 PMID: 24764892

Abstract

In the title solvate, C₁₄H₁₂N₂O·0.5C₆H₆, the complete benzene molecule is generated by a crystallographic inversion centre. The dihedral angle between the planes of the benzimidazole moiety and the phenol substituent is 75.28 (3)°. In the crystal, O—H⋯N hydrogen bonds link the molecules into parallel chains propagating along [100]. The molecules are further connected by C—H⋯π interactions.

Related literature

For related structures, see: Cai et al. (2006 ▶); Rivera et al. (2012 ▶); Shi et al. (2011 ▶). For another synthesis procedure, see: Milata et al. (2001 ▶); Rivera et al. (2008 ▶). For the pharmacological use of benzimidazoles, see: Alamgir et al. (2007 ▶). For C—H⋯π interactions, see: Malathy Sony & Ponnuswamy (2005 ▶).

Experimental

Crystal data

C₁₄H₁₂N₂O·0.5C₆H₆
M _r = 263.31
Triclinic,
a = 8.9351 (11) Å
b = 9.3268 (10) Å
c = 9.9579 (11) Å
α = 73.098 (8)°
β = 69.124 (8)°
γ = 62.148 (8)°
V = 677.75 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 K
0.42 × 0.12 × 0.12 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001 ▶) T _min = 0.967, T _max = 0.990
8981 measured reflections
2591 independent reflections
2314 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.108
S = 1.12
2591 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814000841/sj5381sup1.cif

e-70-0o177-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814000841/sj5381Isup2.hkl

e-70-0o177-Isup2.hkl^{(142.4KB, hkl)}

Click here for additional data file.^{(6.2KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814000841/sj5381Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=981330

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.98 (2)	1.74 (2)	2.7200 (16)	174 (2)
C22—H22⋯Cg1	0.95	3.25	3.868	124

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Symmetry code: (i) Inline graphic .

Acknowledgments

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia, for financial support of this work. LJ-C acknowledges the Vicerrectoría Académica de la Universidad Nacional de Colombia for a fellowship.

supplementary crystallographic information

1. Introduction

Appropriately substituted benzimidazole derivatives have found diverse therapeutic applications as antiulcer, antihypertensive, antiviral, antifungal, anticancer, and antihistaminic agents [Alamgir et al. 2007]. Although the synthesis of the title compound has been reported in the literature (Milata et al., 2001; Rivera et al., 2008), we have developed an alternative route to prepare this compound starting from N¹,N²-bis((1H-benzotriazol-1-yl)methyl)benzene-1,2- diamine.

The asymmetric unit contains one molecule of 2-((1H-benzimidazol-1-yl)methyl)phenol and half a molecule of benzene (Fig. 1). The solvent molecule subtends a dihedral angle of 78.90 (6)° with respect to the phenol substituent and 70.99 (6)° with respect to the benzimidazole moiety, which suggest an edge-to-face (T-shaped) C—H···π interaction according to the literature (Malathy Sony et al. 2005). The dihedral angle between the phenol substitutent and the benzimidazole ring [75.28 (3)°] is similar to the one in a related structure (Cai et al., 2006). In the benzimidazole moiety, the bond distances and angles are in good agreement with those found in bis(1H-benzimidazol-1-yl)methane monohydrate (Shi et al., 2011), 1-(6-chloropyridin-3-ylmethyl)-1H-benzimidazole (Cai et al., 2006) and (1H-benzimidazol-1-yl)methanol (Rivera et al., 2012).

An intermolecular hydrogen bond was observed in the crystal packing (Fig. 2) between the hydroxyl group of one molecule and a nitrogen atom of another one (Table 1). The O—H distance is longer than in (1H-benzimidazol-1-yl)methanol [0.894 (19)Å] (Rivera et al., 2012). However, the O···N distance [2.7200 (16)Å and 2.7355 (16)Å] and the O—H···N angle [174 (2)°, 173.8 (17)°] are similar in both structures. The O—H···N hydrogen bond connects the molecules forming chains running along the a-axis. The benzene molecule is linked to molecules of 2-((1H-benzimidazol-1-yl)methyl)phenol via C—H···π interactions (Fig. 3) acting as both a donor and an acceptor, Table 1. The benzimidazole moiety also forms two C—H···π interactions to the phenol rings of neighbouring molecules. These values are is similar to the values reported for other C—H···π interactions (Malathy Sony et al. 2005).

2. Experimental

2.1. Synthesis and crystallization

A mixture of phenol (0.282 g, 3.00 mmol) and N¹,N²-bis((1H-benzotriazol-1-yl)methyl)benzene-1,2-diamine (0.370 g, 1.00 mmol) was heated to 160 °C, after 5 minutes the mixture was cooled at room temperature until a sticky residue appeared. The product was purified by column chromatography using a mixture of benzene: ethyl acetate (80:20) as the mobile phase (yield 25 %, m.p.= 489-490 K). Single crystals were grown from a benzene:ethyl acetate solution by slow evaporation of the solvent at room temperature over a period of about one week.

2.2. Refinement

All H atoms were located in a difference map. The hydroxyl H atom was freely refined. H atoms bonded to C atoms were refined using a riding model, with secondary C—H = 0.99 Å and aromatic C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C).

3. Results and discussion