1,3-Bis(ethoxy­meth­yl)-1H-benzimidazole-2(3H)-thione

Augusto Rivera; Alexander Mejia-Camacho; Jaime Ríos-Motta; Michal Dušek; Karla Fejfarová

doi:10.1107/S1600536810013036

. 2010 Apr 24;66(Pt 5):o1135–o1136. doi: 10.1107/S1600536810013036

1,3-Bis(ethoxymethyl)-1H-benzimidazole-2(3H)-thione

Augusto Rivera ^a,^*, Alexander Mejia-Camacho ^a, Jaime Ríos-Motta ^a, Michal Dušek ^b, Karla Fejfarová ^b

PMCID: PMC2979012 PMID: 21579184

Abstract

In the structure of the title compound, C₁₃H₁₈N₂O₂S, molecules are linked together by intermolecular C—H⋯S interactions into one-dimensional extended chains along the a axis. The crystal packing is further influenced by weak C—H⋯O interactions.

Related literature

For related structures, see: Odabaşoğlu et al. (2007 ▶). For applications and uses of benzimidazole-2-thiones, see: Zhang et al. (2001 ▶, 2007 ▶); Monforte et al. (2008 ▶); Mazloum et al. (2000 ▶); Perrin & Pagetti (1998 ▶). For chemical background on the synthesis of the title compound, see: Wang & Liu (1996 ▶, 2007 ▶); Rivera & Maldonado (2006 ▶); Rivera et al. (2008 ▶).

Experimental

Crystal data

C₁₃H₁₈N₂O₂S
M _r = 266.4
Monoclinic,
a = 4.7176 (2) Å
b = 16.0664 (6) Å
c = 17.5128 (6) Å
β = 96.524 (3)°
V = 1318.78 (9) Å³
Z = 4
Cu Kα radiation
μ = 2.14 mm⁻¹
T = 120 K
0.36 × 0.09 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.239, T _max = 1.000
11526 measured reflections
2096 independent reflections
1718 reflections with I > 3σ(I)
R _int = 0.035
θ_max = 62.3°

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.110
S = 2.09
2096 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: JANA2006.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013036/bt5233sup1.cif

e-66-o1135-sup1.cif^{(40.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013036/bt5233Isup2.hkl

e-66-o1135-Isup2.hkl^{(99.1KB, 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
C4—H4⋯O2ⁱ	0.95	2.57	3.489 (2)	158.46
C7—H7⋯O1ⁱⁱ	0.95	2.58	3.480 (2)	155.41
C12—H12a⋯S1ⁱⁱⁱ	0.96	2.88	3.7915 (19)	158.58

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

Acknowledgments

The authors acknowledge the Dirección de Investigaciones Sede Bogotá (DIB) of Universidad Nacional de Colombia, the institutional research plan No. AVOZ10100521 of the Institute of Physics and the project Praemium Academiae of the Academy of Sciences of the Czech Republic for financial support.

supplementary crystallographic information

Comment

Benzimidazole-2-thione and their derivatives exhibit potential applications in many areas such as: pharmacological (Zhang et al. 2001, 2007; Monforte et al. 2008) and industrial (Mazloum et al. 2000; Perrin & Pagetti, 1998). This compound has been synthesized by reaction of o-phenylenediamine with carbon disulfide in presence of KOH (Wang & Liu, 2007 ) or tertiary amines (Wang & Liu,1996). Further substitution of heterocyclic system could be obtained by N-alkylation with an alkylating agent. As a part of our research on the structure and properties of aminals cage, we have recently started a study on the reactivity of 6H,13H-5:12,7:14-dimethanedibenzo-[d,i][1,3,6,8]-tetraazecine (DMDBTA) (Rivera et al., 2008, Rivera & Maldonado 2006). In our recent investigation, when we carried out the reaction between DMDBTA and carbon disulfide in ethyl alcohol, the cyclic thiourea 1,3-bis(ethoxymethyl)-1,3-dihydro-2H-benzimidazole-2-thione was obtained and its crystal structure was determined.

The molecular structure of the title compound, a new benzimidazole-2-thione derivative, is shown in Fig. 1. The bond lengths and angles are within normal ranges and are comparable with the related structures (Odabaşoğlu et al., 2007). The crystal structure is further stabilized by intermolecular C—H···S interactions which link neighbouring molecules into 1-D extended chains along the a axis. The interesting feature of the crystal structure is C—H···S distance (2.88 Å), which is shorter than the sum of the Van der Waals radii of S and H by 0.12 Å. A weak intermolecular C—H···O interaction helps to establish the crystal packing which link neighbouring molecules into 1-D extended chains along the b-axis (Fig. 2). This X-ray analysis also shows that both the C8—O1 [1.406 (2) A] and C11—O2 [1.407 (2) A] bonds appear to be shorter than the normal C—O bond-length, whereas the other C—O bond lengths are more agreement with the typical 1.45 Å. This information indicates that the shortening of these bonds suggests some degrees of double bond character.

Experimental

A mixture of CS₂ (0,95 mmol) and DMDBTA (0,95 mmol) in ethanol (30 ml) was stirred at room temperature for 72 hours. After completion of reaction as monitored by TLC the solvent was distilled off in vacuo. The crude residue was purified by column chromatography over silica gel (60-120 mesh), using benzene:ethyl acetate mixture (80:20) as eluent to give the title compound. A suitable single crystal (m.p. 377-379 K) of the product was formed by slow evaporation of an acetone solution at room temperature.

The NMR spectra were acquired at room temperature on a Bruker AMX 400 Advanced spectrometer. ¹H NMR (δ, 399.9 MHz, CDCl₃) δ: 1.18 (6H, t, J=6.7 Hz –CH₃), 3.64 (4H, q, J= 6.7 Hz, O—CH_2-CH₃) 5.82 (4H, s, N—CH₂—O-), 7.27 (2H, m). ¹³C NMR (100 MHz, CDCl₃) δ: 15.0, 64.9, 74.3, 110.1, 123.7, 131.7, 171.8. MS (ESI): [M+H]⁺267.