1-Cyclo­hexyl­methyl-3-methyl-2-[(phenyl­imino)(sulfido)meth­yl]benzimidazolium

Mehmet Akkurt; Selvi Karaca; Hasan Küçükbay; Nihat Şireci; Orhan Büyükgüngör

doi:10.1107/S1600536808008842

. 2008 Apr 10;64(Pt 5):o809. doi: 10.1107/S1600536808008842

1-Cyclohexylmethyl-3-methyl-2-[(phenylimino)(sulfido)methyl]benzimidazolium

Mehmet Akkurt ^a,^*, Selvi Karaca ^a, Hasan Küçükbay ^b, Nihat Şireci ^c, Orhan Büyükgüngör ^d

PMCID: PMC2961076 PMID: 21202300

Abstract

In the zwitterionic title compound, C₂₂H₂₅N₃S, the benzimidazole ring system makes a dihedral angle of 55.69 (11)° with the phenyl ring. In the crystal structure, inter- and intramolecular C—H⋯S interactions occur.

Related literature

For related structures, see: Öztürk et al. (2004 ▶); Akkurt et al. (2005 ▶). For background, see: Allen et al. (1987 ▶); Cremer & Pople (1975 ▶); Küçükbay et al. (1995 ▶); Winberg & Coffman (1965 ▶).

Experimental

Crystal data

C₂₂H₂₅N₃S
M _r = 363.52
Monoclinic,
a = 11.0999 (8) Å
b = 12.4601 (7) Å
c = 15.0143 (14) Å
β = 99.007 (7)°
V = 2051.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 296 K
0.62 × 0.56 × 0.51 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.903, T _max = 0.919
11769 measured reflections
3997 independent reflections
2727 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.127
S = 1.02
3997 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808008842/hb2714sup1.cif

e-64-0o809-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008842/hb2714Isup2.hkl

e-64-0o809-Isup2.hkl^{(191.9KB, 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
C16—H16A⋯S1ⁱ	0.97	2.73	3.683 (2)	167
C16—H16B⋯S1	0.97	2.78	3.451 (2)	127

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDSII diffractometer (purchased under grant F.279 of the University Research Fund). HK and NŞ also thank the İnönü University Research Fund (BAPB-2007–46) for financial support of this study.

supplementary crystallographic information

Comment

Electron-rich olefins are exteremly reactive, powerful π-bases, which are readily converted by aryl isothiocyanates to stable yellow-colored mercapto-N-arylformimidoylimidazolinium orbenzimidazolinium inner salts (zwitterions) in high yield (Winberg & Coffman, 1965; Küçükbay et al., 1995). As part of our onging studies of such materials (Öztürk et al., 2004; Akkurt et al., 2005), we now report the synthesis and structure of the title compound, (I).

The S1—C9 formal single bond of length of 1.6968 (18) Å in (I) is comparable to those reported for similar structures (Öztürk et al., 2004; Akkurt et al., 2005). Otherwise the bond lengths and angles in (I) are normal (Allen et al., 1987). The benzimidazole ring system (N1/N2/C1–C7) is almost planar, with maximum deviations of -0.012 (2) Å for C1 and C6, and makes a dihedral angle of 55.69 (11)° with the phenyl ring (C10–C15). The cyclohexane ring system (C17–C22) has a normal chair conformation [puckering parameters (Cremer & Pople, 1975) are Q_T = 0.554 (3) Å, θ = 175.9 (3)°, φ = 136 (4)°].

In the crystal of (I), the molecules display inter- and intramolecular C—H···S interactions (Table 1, Fig. 2).

Experimental

Phenyl isothiocyanate (0.7 ml, 5. 86 mmol) was added to a solution of bis(1-cyclohexylmethyl-3-methylbenzimidazolidine-2-ylidene) (1.1 g, 2.41 mmol) in toluene (15 ml) and the mixture was stirred at room temperature for 2 h. A yellow solid was precipitated in solution. The precipitate was filtered and recrystallized in EtOH / DMF to yield yellow blocks of (I). (Yield: 1.49 g, 85%. m.p.:463–465 K). ¹H NMR (DMSO-d₆,δ, p.p.m.): 1.11 (s, ring methylene, 6H), 1.59 (d, ring methylene, 4H), 2.09 (s, ring methylene, 1H), 4.04 (s, CH₃, 3H), 4.45 (d, –CH₂—N, 2H), 7.22 (m, Ar—H (forPhNCS), 5H), 7.93 (m, Ar—H, 4H); ¹³C NMR (DMSO-d₆, δ,p.p.m.): 25.10, 25.15, 30.05, 30.12,38.05, 50.03, 112.11, 122.04, 122.10, 126.01, 129.03, 129.14, 131.23, 149.06,151.34, 167.44. Analysis calculated for C₂₂H₂₅N₃S: C 72.72, H 6.88, N 11.57, S 8.81%; found: C 71.82, H 6.87, N 11.46, S 8.22%.