2-(1H-1,3-Benzodiazol-2-ylsulfan­yl)-1-(4-chloro­phen­yl)ethanone

Hatem A Abdel-Aziz; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S160053681103666X

. 2011 Sep 14;67(Pt 10):o2639. doi: 10.1107/S160053681103666X

2-(1H-1,3-Benzodiazol-2-ylsulfanyl)-1-(4-chlorophenyl)ethanone

Hatem A Abdel-Aziz ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3201531 PMID: 22064924

Abstract

The molecule in the structure of the title compound, C₁₅H₁₁ClN₂OS, displays two planar residues [r.m.s. deviation = 0.014 Å for the benzimidazole residue, and the ketone group is co-planar with the benzene ring to which it is attached forming a O—C—C—C torsion angle of −173.18 (14) °] linked at the S atom. The overall shape is based on a twisted V, the dihedral angle formed between the two planes being 82.4 (2) °. The amine-H atom is bifurcated, forming N—H⋯O and N—H⋯S hydrogen bonds leading to dimeric aggregates. These are linked into a supramolecular chain along the c axis via C—H⋯π hydrogen bonds. Chains form layers in the ab plane being connected along the c axis via weak π–π interactions [3.9578 (8) Å] formed between centrosymmetrically related chloro-substituted benzene rings.

Related literature

For the biological and pharmacological properties of benzimidazoles, see: Al-Rashood & Abdel-Aziz (2010 ▶); Abdel-Aziz et al. (2010 ▶). For the synthesis, see: Sarhan et al. (1996 ▶). For a related structure, see: Lynch & McClenaghan (2004 ▶).

Experimental

Crystal data

C₁₅H₁₁ClN₂OS
M _r = 302.77
Monoclinic,
a = 27.3765 (4) Å
b = 9.2784 (2) Å
c = 10.3630 (2) Å
β = 93.087 (1)°
V = 2628.49 (9) Å³
Z = 8
Cu Kα radiation
μ = 4.02 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.710, T _max = 1.000
5171 measured reflections
2613 independent reflections
2489 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.079
S = 1.07
2613 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681103666X/ez2258sup1.cif

e-67-o2639-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103666X/ez2258Isup2.hkl

e-67-o2639-Isup2.hkl^{(128.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681103666X/ez2258Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C10–C15 and N1,N2,C1,C6,C7 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.88 (2)	2.14 (2)	2.9104 (16)	144.9 (19)
N2—H2⋯S1ⁱ	0.88 (2)	2.69 (2)	3.4073 (12)	139.1 (16)
C8—H8a⋯Cg1ⁱⁱ	0.99	2.89	3.5678 (15)	126
C8—H8b⋯Cg2ⁱⁱⁱ	0.99	2.76	3.4204 (16)	125

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

Acknowledgments

The authors thank King Saud University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The structural analysis of the title compound, (I), is motivated by recent studies into the biological potential of benzimidazoles (Al-Rashood & Abdel-Aziz, 2010; Abdel-Aziz et al., 2010). The molecule of (I), Fig. 1, has a twisted V-shape. As expected, the benzimidazole residue is planar (r.m.s. deviation = 0.014 Å). The ketone group is co-planar with the benzene ring to which it is attached as seen in the value of the O1—C9—C10—C11 torsion angle of -173.18 (14) °. As the S1—C8—C9—O1 torsion angle is -0.39 (18) °, the molecule comprises two planar residues that form a dihedral angle of 82.4 (2) °. The most closely related structure in the literature is that of 2-(benzoylmethylsulfanyl)-6-methoxy-1H-benzimidazole (Lynch & McClenaghan, 2004), i.e. with a methoxy substituent on the benzene ring of the benzimidazole and no substituent on the ring attached to the ketone. This adopts a similar conformation with the ketone benzene ring inclined to the benzimidazole residue with the dihedral angle formed between the ring systems being 67.13 (9) °.

In the crystal packing two molecules, related by a 2-fold axis of symmetry associate via N—H···O and N—H···S hydrogen bonds as the amine-H atom is bifurcated, Table 1. As seen from Fig. 2, this results in the formation of two S(5), {···H···OC₂S} ring motifs which flank a central eight-membered {···HNCS}₂ synthon. The dimeric aggregates are linked into a supramolecular chain along the c axis via C—H···π interactions Table 1 and Fig. 3. Chains assemble into layers in the ab plane and are connected along the c axis via weak π···π interactions of 3.9578 (8) Å formed between the chloro-substituted benzene rings (C10–C15); symmetry operation: 1/2 - x, 1/2 - y, 1 - z, Fig. 4.

Experimental

The reaction of 2-mercaptobenzimidazole with 4-chloroacetophenone in boiling AcOH/H₂SO₄ afforded the sulfate salt of 2-(1H-benzo[d]imidazol-2-ylthio)-1-(4-chlorophenyl)ethanone after Sarhan et al. (1996). Neutralization of the latter salt afforded the title compound and the light-brown crystals were grown from its ethanol solution by slow evaporation at room temperature.