4-[1-(4-Cyano­benz­yl)-1H-benzimidazol-2-yl]benzonitrile

Reza Kia; Hoong-Kun Fun; Hadi Kargar

doi:10.1107/S1600536809006989

. 2009 Mar 6;65(Pt 4):o660–o661. doi: 10.1107/S1600536809006989

4-[1-(4-Cyanobenzyl)-1H-benzimidazol-2-yl]benzonitrile

Reza Kia ^a, Hoong-Kun Fun ^a,^*, Hadi Kargar ^b

PMCID: PMC2969064 PMID: 21582406

Abstract

In the title compound, C₂₂H₁₄N₄, a new substituted benzimidazole, three intermolecular C—H⋯N interactions link neighbouring molecules into different dimers with R ₂ ²(12), R ₂ ²(8) and R ₂ ²(24) ring motifs. A fourth C—H⋯N interaction links neighbouring molecules along the c axis. There is also a short intermolecular contact between the azomethine (C=N) segment of the benzimidazole ring and one of the C atoms of a neighbouring benzene ring [N⋯C = 3.191 (5), C⋯C = 3.364 (6) Å], which links the molecules along the a axis. The two cyanobenzene rings are almost perpendicular to each other, with an interplanar angle of 87.70 (7)°. The dihedral angles between the mean planes of the benzimidazole ring and the two outer benzene rings are 36.27 (16) and 86.70 (16)°. In the crystal structure, molecules are stacked down the a axis with centroid–centroid distances of 3.906 (2)–3.912 (2) Å and interplanar distances of 3.5040 (17) and 3.6235 (17) Å.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For benzimidazole chemistry, reaction mechanisms and their bioactivity, see, for example: Latif et al. (1983 ▶); Craigo et al. (1999 ▶); Gudmundsson et al. (2000 ▶); Trivedi et al. (2006); Kim et al. (1996 ▶); Ramla et al. (2006 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₂H₁₄N₄
M _r = 334.37
Monoclinic,
a = 5.0553 (4) Å
b = 17.3437 (10) Å
c = 19.6339 (14) Å
β = 97.653 (5)°
V = 1706.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.45 × 0.09 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.965, T _max = 0.997
15641 measured reflections
2906 independent reflections
1490 reflections with I > 2σ(I)
R _int = 0.153

Refinement

R[F ² > 2σ(F ²)] = 0.079
wR(F ²) = 0.169
S = 1.07
2906 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006989/zl2173sup1.cif

e-65-0o660-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006989/zl2173Isup2.hkl

e-65-0o660-Isup2.hkl^{(142.7KB, 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
C12—H12A⋯N1ⁱ	0.93	2.62	3.425 (5)	146
C19—H19A⋯N4ⁱⁱ	0.93	2.57	3.502 (6)	175
C9—H9A⋯N4ⁱⁱⁱ	0.93	2.71	3.361 (5)	128
C14—H14A⋯N3^iv	0.97	2.57	3.502 (5)	162

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HK thanks PNU for financial support. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Benzimidazoles are used widely in biological applications and as pharmaceutical agents (Craigo et al., 1999; Gudmundsson et al., 2000; Trivedi et al., 2006). They are also used as topoisomerase I inhibitors (Kim et al., 1996) and for antitumor activity (Ramla et al., 2006). Due to these important applications, many synthetic routes towards benzimidazoles have been developed. They can, for example, be synthesized by the reaction of phenolic aldehydes with o-phenylenediamine (Latif et al., 1983). Based on this route the title compound was synthesized and its crystal structure is reported here.

The title compound, Fig.1, comprises a single molecule in the asymmetric unit. Three intermolecular C—H···N interactions link neighbouring molecules into different dimers with R₂²(12), R₂²(8) and R₂²(24) ring motifs (Bernstein et al., 1995). A fourth C—H···N interaction links neighbouring molecules along the c axis. The two cyanobenzene rings are almost perpendicular to each other, with an interplanar angle of 87.70 (7)°. The dihedral angles between the the mean planes of the benzimidazole ring and the two outer benzene rings are 36.27 (16) and 86.70 (16)°. There is also a short intermolecular contact between the azomethine (C1═N1) segment of the benzimidazole ring and one of the carbon atoms (C13) of the neighbouring benzene rings which links the molecules along the a axis (N1···C13^v = 3.191 (5) C1···C13^v = 3.364 (6), symmetry code: (v) x-1, y, z). In the crystal structure, the molecules are stacked down the a axis with centroid to centroid distances of 3.906 (2)–3.912 (2) Å and interplanar distances of 3.5040 (17) and 3.6235 (17) Å [Cg1···Cg2^vi = 3.906 (2); (vi) 1 + x, y, z and Cg1···Cg3^vii = 3.912 (2) Å; (vii) -1 + x, y, z: Cg1, Cg2 and Cg3 are the centroids of the N1/C1/C6/N2/C7, C1–C6, and C8–C13 benzene rings] (Fig. 2).

Experimental

An ethanolic solution (50 ml) of 4-cyanobenzaldehyde (2 mmol, 263 mg) was added to 1,2-phenylenediamine (1 mmol, 217 mg). The mixture was refluxed for 2 h, and cooled to room temperature. The resulting colourless powder was filtered, washed with cooled ethanol and dried in vacuo. Single crystals suitable for X-ray diffraction were obtained from an ethanol solution at room temperature.