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Acta Cryst. (2008). E64, o809    [ doi:10.1107/S1600536808008842 ]

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

M. Akkurt, S. Karaca, H. Küçükbay, N. Sireci and O. Büyükgüngör

Abstract top

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.

Comment top

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 QT = 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).

Related literature top

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 top

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%.

Refinement top

All H atoms were placed in calculated positions and refined as riding with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 or 1.5Ueq(C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); 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).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I) showing 20% displacement ellipsoids for the non-H atoms.
[Figure 2] Fig. 2. View of the packing and intermolecular C—H···S hydrogen bond contacts in the unit cell of (I).
1-cyclohexylmethyl-3-methyl-2-[(phenylimino)(sulfido)methyl]benzimidazolium top
Crystal data top
C22H25N3SF000 = 776
Mr = 363.52Dx = 1.177 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12543 reflections
a = 11.0999 (8) Åθ = 1.4–28.0º
b = 12.4601 (7) ŵ = 0.17 mm−1
c = 15.0143 (14) ÅT = 296 K
β = 99.007 (7)ºBlock, yellow
V = 2051.0 (3) Å30.62 × 0.56 × 0.51 mm
Z = 4
Data collection top
Stoe IPDSII
diffractometer		3997 independent reflections
Monochromator: plane graphite2727 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm-1Rint = 0.031
T = 296 Kθmax = 26.0º
ω scansθmin = 1.9º
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		h = −13→13
Tmin = 0.903, Tmax = 0.919k = −15→13
11769 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.127  w = 1/[σ2(Fo2) + (0.0746P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3997 reflectionsΔρmax = 0.36 e Å−3
236 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C22H25N3SV = 2051.0 (3) Å3
Mr = 363.52Z = 4
Monoclinic, P21/cMo Kα
a = 11.0999 (8) ŵ = 0.17 mm−1
b = 12.4601 (7) ÅT = 296 K
c = 15.0143 (14) Å0.62 × 0.56 × 0.51 mm
β = 99.007 (7)º
Data collection top
Stoe IPDSII
diffractometer		3997 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		2727 reflections with I > 2σ(I)
Tmin = 0.903, Tmax = 0.919Rint = 0.031
11769 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046236 parameters
wR(F2) = 0.127H-atom parameters constrained
S = 1.02Δρmax = 0.36 e Å−3
3997 reflectionsΔρmin = −0.37 e Å−3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.40319 (5)0.79425 (5)0.26689 (5)0.0886 (2)
N10.28968 (12)0.63297 (12)0.44357 (9)0.0502 (5)
N20.34915 (12)0.54355 (11)0.33351 (9)0.0487 (4)
N30.16469 (13)0.75498 (13)0.28359 (10)0.0572 (5)
C10.32300 (14)0.53150 (14)0.47690 (11)0.0503 (6)
C20.32500 (17)0.48719 (19)0.56177 (13)0.0650 (7)
C30.36543 (19)0.3831 (2)0.57255 (16)0.0738 (8)
C40.40346 (18)0.32577 (18)0.50294 (17)0.0738 (8)
C50.40103 (17)0.36931 (16)0.41825 (15)0.0632 (7)
C60.36035 (14)0.47437 (14)0.40713 (12)0.0494 (5)
C70.30640 (14)0.63806 (14)0.35726 (11)0.0465 (5)
C80.2483 (2)0.72060 (18)0.49579 (14)0.0687 (7)
C90.27958 (15)0.73442 (14)0.29906 (11)0.0507 (5)
C100.11976 (17)0.84557 (17)0.23179 (13)0.0614 (6)
C110.1515 (2)0.94910 (19)0.25693 (16)0.0791 (8)
C120.0936 (3)1.0351 (2)0.2082 (2)0.1043 (11)
C130.0082 (3)1.0155 (4)0.1341 (3)0.1179 (14)
C14−0.0228 (3)0.9139 (4)0.1091 (2)0.1084 (13)
C150.03093 (19)0.8291 (2)0.15829 (15)0.0815 (9)
C160.38428 (16)0.51876 (17)0.24565 (12)0.0577 (6)
C170.27793 (17)0.49794 (17)0.17240 (12)0.0612 (7)
C180.3246 (2)0.4812 (2)0.08393 (14)0.0816 (9)
C190.2221 (3)0.4596 (3)0.00661 (17)0.1112 (15)
C200.1411 (3)0.3698 (3)0.02668 (19)0.1048 (11)
C210.0958 (3)0.3852 (3)0.1148 (2)0.1050 (11)
C220.2009 (2)0.4028 (2)0.19119 (16)0.0819 (9)
H20.300400.525800.608800.0780*
H30.367300.350100.628300.0890*
H40.431400.255900.513600.0890*
H50.425300.330400.371300.0760*
H8A0.259700.787700.466800.0830*
H8B0.294500.720600.555400.0830*
H8C0.163300.711100.499400.0830*
H110.211400.961900.306400.0950*
H120.113001.105200.226000.1250*
H13−0.028901.072700.100600.1410*
H14−0.080800.901400.058300.1300*
H150.007000.759500.141700.0980*
H16A0.436600.456000.252000.0690*
H16B0.431300.578300.227500.0690*
H170.225800.561800.166500.0730*
H18A0.380800.421100.089900.0980*
H18B0.369000.544600.070300.0980*
H19A0.173600.52420−0.005900.1330*
H19B0.256800.44200−0.047000.1330*
H20A0.185800.302800.028300.1260*
H20B0.071900.36490−0.021400.1260*
H21A0.049800.322400.127700.1260*
H21B0.041600.446600.110500.1260*
H22A0.169000.414900.246900.0980*
H22B0.251400.338900.198800.0980*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0631 (3)0.0819 (4)0.1212 (5)−0.0041 (3)0.0155 (3)0.0461 (4)
N10.0531 (7)0.0518 (9)0.0451 (8)−0.0037 (6)0.0063 (6)0.0022 (7)
N20.0498 (7)0.0496 (8)0.0461 (8)0.0028 (6)0.0061 (6)0.0030 (6)
N30.0568 (8)0.0579 (9)0.0562 (9)0.0096 (7)0.0069 (7)0.0065 (7)
C10.0478 (8)0.0543 (11)0.0468 (10)−0.0099 (7)0.0015 (7)0.0064 (8)
C20.0643 (11)0.0787 (14)0.0501 (11)−0.0184 (10)0.0035 (8)0.0113 (10)
C30.0692 (12)0.0802 (16)0.0676 (13)−0.0205 (11)−0.0033 (10)0.0307 (12)
C40.0626 (11)0.0596 (12)0.0941 (17)−0.0073 (9)−0.0038 (11)0.0271 (12)
C50.0598 (10)0.0516 (11)0.0762 (13)−0.0010 (8)0.0049 (9)0.0094 (10)
C60.0446 (8)0.0500 (10)0.0515 (10)−0.0047 (7)0.0008 (7)0.0094 (8)
C70.0443 (8)0.0503 (10)0.0441 (9)−0.0025 (7)0.0047 (6)0.0023 (7)
C80.0832 (13)0.0683 (14)0.0568 (11)0.0026 (10)0.0175 (9)−0.0095 (10)
C90.0565 (9)0.0501 (10)0.0443 (9)0.0013 (7)0.0044 (7)0.0030 (8)
C100.0633 (10)0.0690 (13)0.0535 (10)0.0197 (9)0.0143 (8)0.0077 (10)
C110.1043 (16)0.0682 (15)0.0667 (13)0.0194 (12)0.0196 (12)0.0080 (11)
C120.133 (2)0.0744 (17)0.117 (2)0.0412 (16)0.055 (2)0.0263 (16)
C130.110 (2)0.147 (3)0.104 (2)0.073 (2)0.0394 (18)0.062 (2)
C140.0856 (17)0.159 (3)0.0791 (17)0.052 (2)0.0083 (13)0.029 (2)
C150.0686 (12)0.1101 (19)0.0644 (13)0.0266 (12)0.0061 (10)0.0061 (13)
C160.0604 (10)0.0609 (12)0.0541 (10)0.0051 (8)0.0165 (8)0.0017 (9)
C170.0694 (11)0.0609 (12)0.0528 (11)0.0152 (9)0.0077 (8)−0.0019 (9)
C180.1018 (16)0.0905 (17)0.0537 (12)0.0079 (13)0.0156 (11)0.0038 (12)
C190.141 (3)0.133 (3)0.0545 (14)0.023 (2)−0.0003 (15)0.0003 (15)
C200.114 (2)0.105 (2)0.0840 (18)0.0193 (17)−0.0204 (16)−0.0297 (16)
C210.0878 (16)0.127 (2)0.0957 (19)−0.0097 (15)0.0007 (14)−0.0336 (18)
C220.0780 (14)0.0992 (18)0.0685 (14)−0.0149 (12)0.0116 (11)−0.0101 (13)
Geometric parameters (Å, °) top
S1—C91.6968 (18)C20—C211.500 (4)
N1—C11.388 (2)C21—C221.518 (4)
N1—C71.339 (2)C2—H20.9300
N1—C81.460 (3)C3—H30.9300
N2—C61.392 (2)C4—H40.9300
N2—C71.339 (2)C5—H50.9300
N2—C161.466 (2)C8—H8A0.9600
N3—C91.286 (2)C8—H8B0.9600
N3—C101.416 (3)C8—H8C0.9600
C1—C21.386 (3)C11—H110.9300
C1—C61.383 (2)C12—H120.9300
C2—C31.374 (3)C13—H130.9300
C3—C41.385 (3)C14—H140.9300
C4—C51.379 (3)C15—H150.9300
C5—C61.386 (3)C16—H16A0.9700
C7—C91.487 (2)C16—H16B0.9700
C10—C111.374 (3)C17—H170.9800
C10—C151.375 (3)C18—H18A0.9700
C11—C121.396 (4)C18—H18B0.9700
C12—C131.366 (5)C19—H19A0.9700
C13—C141.350 (7)C19—H19B0.9700
C14—C151.371 (5)C20—H20A0.9700
C16—C171.505 (3)C20—H20B0.9700
C17—C181.514 (3)C21—H21A0.9700
C17—C221.514 (3)C21—H21B0.9700
C18—C191.517 (4)C22—H22A0.9700
C19—C201.495 (5)C22—H22B0.9700
C1—N1—C7108.81 (14)N1—C8—H8B110.00
C1—N1—C8125.17 (14)N1—C8—H8C109.00
C7—N1—C8125.97 (15)H8A—C8—H8B110.00
C6—N2—C7108.94 (14)H8A—C8—H8C109.00
C6—N2—C16125.52 (15)H8B—C8—H8C109.00
C7—N2—C16125.48 (15)C10—C11—H11120.00
C9—N3—C10120.80 (16)C12—C11—H11120.00
N1—C1—C2131.24 (17)C11—C12—H12120.00
N1—C1—C6106.88 (14)C13—C12—H12120.00
C2—C1—C6121.87 (17)C12—C13—H13120.00
C1—C2—C3116.26 (19)C14—C13—H13120.00
C2—C3—C4122.0 (2)C13—C14—H14120.00
C3—C4—C5121.9 (2)C15—C14—H14120.00
C4—C5—C6116.21 (19)C10—C15—H15120.00
N2—C6—C1106.42 (15)C14—C15—H15120.00
N2—C6—C5131.86 (17)N2—C16—H16A109.00
C1—C6—C5121.70 (17)N2—C16—H16B109.00
N1—C7—N2108.95 (15)C17—C16—H16A109.00
N1—C7—C9124.16 (15)C17—C16—H16B109.00
N2—C7—C9126.89 (15)H16A—C16—H16B108.00
S1—C9—N3133.19 (14)C16—C17—H17108.00
S1—C9—C7115.18 (12)C18—C17—H17108.00
N3—C9—C7111.63 (15)C22—C17—H17108.00
N3—C10—C11122.96 (18)C17—C18—H18A109.00
N3—C10—C15117.92 (19)C17—C18—H18B109.00
C11—C10—C15118.8 (2)C19—C18—H18A109.00
C10—C11—C12120.0 (2)C19—C18—H18B109.00
C11—C12—C13119.6 (3)H18A—C18—H18B108.00
C12—C13—C14120.6 (4)C18—C19—H19A109.00
C13—C14—C15120.2 (3)C18—C19—H19B109.00
C10—C15—C14120.9 (3)C20—C19—H19A109.00
N2—C16—C17113.91 (15)C20—C19—H19B109.00
C16—C17—C18109.15 (16)H19A—C19—H19B108.00
C16—C17—C22113.59 (17)C19—C20—H20A109.00
C18—C17—C22109.66 (18)C19—C20—H20B109.00
C17—C18—C19112.2 (2)C21—C20—H20A109.00
C18—C19—C20112.4 (2)C21—C20—H20B109.00
C19—C20—C21112.2 (3)H20A—C20—H20B108.00
C20—C21—C22111.2 (3)C20—C21—H21A109.00
C17—C22—C21111.2 (2)C20—C21—H21B109.00
C1—C2—H2122.00C22—C21—H21A109.00
C3—C2—H2122.00C22—C21—H21B109.00
C2—C3—H3119.00H21A—C21—H21B108.00
C4—C3—H3119.00C17—C22—H22A109.00
C3—C4—H4119.00C17—C22—H22B109.00
C5—C4—H4119.00C21—C22—H22A109.00
C4—C5—H5122.00C21—C22—H22B109.00
C6—C5—H5122.00H22A—C22—H22B108.00
N1—C8—H8A109.00
C7—N1—C1—C2178.50 (18)C1—C2—C3—C40.7 (3)
C8—N1—C1—C20.9 (3)C2—C3—C4—C5−1.1 (3)
C7—N1—C1—C6−0.28 (18)C3—C4—C5—C61.1 (3)
C8—N1—C1—C6−177.88 (16)C4—C5—C6—C1−0.8 (3)
C1—N1—C7—N20.09 (19)C4—C5—C6—N2177.97 (18)
C8—N1—C7—N2177.66 (16)N2—C7—C9—N3112.86 (19)
C1—N1—C7—C9179.56 (15)N1—C7—C9—S1113.46 (16)
C8—N1—C7—C9−2.9 (3)N1—C7—C9—N3−66.5 (2)
C6—N2—C7—N10.14 (18)N2—C7—C9—S1−67.2 (2)
C16—N2—C7—N1−177.02 (15)N3—C10—C11—C12−172.9 (2)
C6—N2—C7—C9−179.31 (15)C11—C10—C15—C141.9 (3)
C16—N2—C7—C93.5 (3)C15—C10—C11—C120.2 (3)
C6—N2—C16—C17105.6 (2)N3—C10—C15—C14175.3 (2)
C7—N2—C16—C17−77.7 (2)C10—C11—C12—C13−2.0 (4)
C7—N2—C6—C5−179.20 (18)C11—C12—C13—C141.7 (5)
C7—N2—C6—C1−0.31 (18)C12—C13—C14—C150.3 (5)
C16—N2—C6—C1176.85 (15)C13—C14—C15—C10−2.2 (4)
C16—N2—C6—C5−2.0 (3)N2—C16—C17—C18176.01 (17)
C9—N3—C10—C11−61.4 (3)N2—C16—C17—C22−61.3 (2)
C9—N3—C10—C15125.6 (2)C16—C17—C18—C19180.0 (2)
C10—N3—C9—S1−2.0 (3)C22—C17—C18—C1954.9 (3)
C10—N3—C9—C7178.02 (15)C16—C17—C22—C21−179.6 (2)
N1—C1—C6—N20.36 (18)C18—C17—C22—C21−57.1 (3)
C6—C1—C2—C3−0.4 (3)C17—C18—C19—C20−52.9 (3)
N1—C1—C2—C3−179.03 (18)C18—C19—C20—C2152.0 (4)
N1—C1—C6—C5179.38 (16)C19—C20—C21—C22−54.1 (4)
C2—C1—C6—N2−178.56 (16)C20—C21—C22—C1757.1 (3)
C2—C1—C6—C50.5 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···S1i0.972.733.683 (2)167
C16—H16B···S10.972.783.451 (2)127
Symmetry codes: (i) −x+1, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···S1i0.972.733.683 (2)167
C16—H16B···S10.972.783.451 (2)127
Symmetry codes: (i) −x+1, y−1/2, −z+1/2.
Acknowledgements top

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.

references
References top

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