Bis{2-[4-(methyl­sulfan­yl)phen­yl]-1H-benzimidazol-3-ium} tetra­bromido­cuprate(II) dihydrate

M N Manjunatha; Mohamed Ziaulla; Ravish Sankolli; Noor Shahina Begum; K R Nagasundara

doi:10.1107/S1600536811012840

. 2011 Apr 13;67(Pt 5):m578. doi: 10.1107/S1600536811012840

Bis{2-[4-(methylsulfanyl)phenyl]-1H-benzimidazol-3-ium} tetrabromidocuprate(II) dihydrate

M N Manjunatha ^a, Mohamed Ziaulla ^a, Ravish Sankolli ^b, Noor Shahina Begum ^a,^*, K R Nagasundara ^a

PMCID: PMC3089137 PMID: 21754304

Abstract

The asymmetric unit of the title compound, (C₁₄H₁₃N₂S)₂[CuBr₄]·2H₂O, contains two cations, one anion and two solvent water molecules that are connected via O—H⋯Br, N—H⋯Br and N—H⋯O hydrogen bonds into a two-dimensional polymeric structure. The cations are arranged in a head-to-tail fashion and form stacks along [100]. The central Cu^II atom of the anion is in a distorted tetrahedral environment.

Related literature

For general background to benzimidazoles and their derivatives, see: Huang & Scarborough et al. (1999 ▶); Preston (1974 ▶); Zhu et al. (2000 ▶). For related structures, see: Ziaulla et al. (2011 ▶).

Experimental

Crystal data

(C₁₄H₁₃N₂S)₂[CuBr₄]·2H₂O
M _r = 901.86
Triclinic,
a = 7.6878 (5) Å
b = 11.8358 (7) Å
c = 18.5485 (9) Å
α = 85.305 (4)°
β = 84.778 (5)°
γ = 80.692 (5)°
V = 1654.74 (17) Å³
Z = 2
Mo Kα radiation
μ = 5.65 mm⁻¹
T = 296 K
0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.430, T _max = 0.465
27134 measured reflections
5805 independent reflections
3344 reflections with I > 2σ(I)
R _int = 0.110

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.127
S = 1.00
5805 reflections
384 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012840/gk2356sup1.cif

e-67-0m578-sup1.cif^{(33.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012840/gk2356Isup2.hkl

e-67-0m578-Isup2.hkl^{(278.4KB, 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
N3—H3⋯O1ⁱ	0.86	1.86	2.703 (8)	165
N2—H2⋯Br3ⁱⁱ	0.86	2.44	3.275 (6)	162
O1—H1D⋯Br3ⁱⁱⁱ	0.85 (6)	2.55 (7)	3.344 (6)	155
O2—H2A⋯Br2ⁱⁱⁱ	0.83 (4)	2.96 (6)	3.735 (6)	155
O1—H1E⋯Br1	0.84 (7)	2.53 (7)	3.359 (6)	170
O2—H2B⋯Br4	0.85 (5)	2.77 (7)	3.597 (6)	166

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

Acknowledgments

NSB is thankful to the University Grants Commission (UGC), India, for financial assistance and the Department of Science and Technology, (DST), India, for the data collection facility under the IRHPA–DST program. MNM thanks the M. S. Ramaiah Institute of Technology, Bangalore, for their support and encouragement.

supplementary crystallographic information

Comment

The synthesis of benzimidazoles makes use of solid-phase synthesis via o-nitroanilines (Preston et al., 1974; Huang &Scarborough, 1999). Benzimidazole derivatives are effective against the human cytomegalo virus (HCMV) (Zhu et al., 2000). In addition benzimidazole derivatives exhibit a number of important pharmacological properties, such as antihistaminic, anti-ulcerative, antiallergic and antipyretic. In the title compound, as shown in Fig. 1, there are two cations, one tetrabromidocopper(II) anion and two solvent water molecules in the asymmetric unit. The Cu^II atom shows strongly distorted tetrahedral geometry, coordinating with four terminal bromine atoms with the bond lengths in the range 2.3389 (1) Å to 2.4084 (1) Å. The Br—Cu—Br bond angles are between 96.18 (4)° and 139.53 (6)°. The benzimidazole and thiomethyl phenyl rings are virtually planar and inclined at an dihedral angle 2.67 (2)° . The bond lengths and angles for the benzimidazole cation of the molecule are in good agreement, within experimental errors, with those observed in other benzimidazole derivatives (Ziaulla et al., 2011). The crystal structure is stabilized by N—H···O, O—H···Br and N—H···Br hydrogen bonds (Fig.2).

Experimental

An ethanolic solution (15 ml) of the 2-(4-methylsulfanyl phenyl)-1H- benzimidazole) (0.960 g, 2 mmol) was added to a solution of copper(II) bromide (0.446 g, 1 mmol) in ethanol (25 ml). The mixture was then treated with 48% HBr (2–3 ml) followed by liquid Br2 (2–3 ml).The mixture was refluxed for nearly six hours during which yellow crystals suitable for X-ray analysis were obtained. The crystals were washed with cold ethanol and dried in vacuum over P₂O₅ (yield 1.2 g, 85%).