1,3-Bis(3-phenyl­prop­yl)-1H-benzimidazol-3-ium-2-carbodithio­ate

Mehmet Akkurt; Ülkü Yılmaz; Hasan Küçükbay; Mustafa Gençaslan; Orhan Büyükgüngör

doi:10.1107/S1600536808042761

. 2008 Dec 20;65(Pt 1):o174–o175. doi: 10.1107/S1600536808042761

1,3-Bis(3-phenylpropyl)-1H-benzimidazol-3-ium-2-carbodithioate

Mehmet Akkurt ^a,^*, Ülkü Yılmaz ^b, Hasan Küçükbay ^b, Mustafa Gençaslan ^a, Orhan Büyükgüngör ^c

PMCID: PMC2968085 PMID: 21581631

Abstract

The title compound, C₂₆H₂₆N₂S₂, was synthesized from bis[1,3-bis(3-phenylpropyl)benzimidazolidine-2-ylidene] and CS₂ in toluene. The molecular structure is composed of a benzimidazole ring system with two phenylpropyl substituents and a dithiocarboxylate group in the 2-position. The benzimidazole unit is essentially planar, with a maximum atomic deviation of 0.008 (2) Å, and makes dihedral angles of 72.72 (10) and 27.62 (12)°, with the two phenyl rings. The dihedral angle between the two phenyl rings is 55.98 (15)°. The molecular packing is stabilized by a C—H⋯S intermolecular hydrogen-bonding interaction and a C—H⋯π interaction between a benzene H atom and the phenyl ring of a neighbouring molecule.

Related literature

For applications of benzimidazole derivatives, see: Hahn & Jahnke (2008 ▶); Lappert (2005 ▶); Winberg & Coffman (1965 ▶); Küçükbay et al. (1996 ▶, 1997 ▶); Çetinkaya et al. (1994 ▶, 1998 ▶). For details of the synthesis, see: Yılmaz (2008 ▶). For related structures, see: Akkurt et al. (2004 ▶, 2005 ▶); Öztürk et al. (2003 ▶, 2004 ▶).

Experimental

Crystal data

C₂₆H₂₆N₂S₂
M _r = 430.63
Orthorhombic,
a = 27.2391 (11) Å
b = 8.3483 (4) Å
c = 10.3200 (4) Å
V = 2346.77 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 (2) K
0.76 × 0.65 × 0.38 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.838, T _max = 0.914
19766 measured reflections
4983 independent reflections
3842 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.080
S = 0.97
4983 reflections
271 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ▶), 2317 Friedel pairs
Flack parameter: −0.03 (5)

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/S1600536808042761/kj2110sup1.cif

e-65-0o174-sup1.cif^{(27.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042761/kj2110Isup2.hkl

e-65-0o174-Isup2.hkl^{(239.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

C8—S1	1.6670 (18)
C8—S2	1.6532 (18)
C1—N1	1.393 (2)
C7—N2	1.341 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19B⋯S2ⁱ	0.97	2.87	3.680 (2)	142
C5—H5⋯Cg1ⁱⁱ	0.93	2.70	3.523 (2)	148

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C12–C17 phenyl ring.

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS-2 diffractometer (purchased under grant F.279 of the University Research Fund). HK and ÜY thank the İnönü University Research Fund (Directed project BAPB-2008/59) for financial support of this study.

supplementary crystallographic information

Comment

Benzimidazole derivatives consistute an important class of heterocyclic compounds for their biological activities. They also are an important source for electron-rich olefin synthesis. Electron rich olefins are an important research subject for their versatile reactions. Since electron rich olefins are powerful nucleophilic compounds, they have been used as reducing agents, and are a source of carbine transation metal complexes and formylating agents for the proton active compounds (Hahn & Jahnke, 2008; Lappert, 2005). They are readily converted by carbon disulfide to red coloured stable dithioquaternary salts. (Winberg & Coffman,1965). Electron rich olefins have also been used as catalysts for cyloin type C—C coupling reactions. In a number of previous papers (Çetinkaya et al., 1994; Küçükbay et al., 1996; Küçükbay et al., 1997; Çetinkaya, et al., 1998) we reported the synthesis of some benzimidazole derived electron rich olefins.

The objective of this study was to elucidate the crystal structure of the title compound and to compare it with those of related benzimidazole derivatives reported previously (Akkurt et al., 2004; Öztürk et al., 2004; Akkurt et al., 2005).

The ORTEP diagram of the title molecule with numbering scheme is shown in Fig. 1. The molecular structure of the title compound is composed of a benzimidazole ring with two phenylpropyl substituents and a dithiocarboxylate group in the 2-position. In the title molecule the C–S bonds are nearly equal in length. The N1–C7 and N2–C7 bond lengths in the benzimidazole ring agree well with several related benzimidazole derivatives (Öztürk et al., 2003; Akkurt et al., 2004). The benzimidazole unit (N1/N2/C1–C7) is essentially, with a maximum deviation from the least-squares plane of 0.008 (2) Å for C6. The benzimidazole ring makes dihedral angles of 72.72 (10) and 27.62 (12)°, with the two phenyl rings (C12–C17) and (C21–C26), respectively. The dihedral angle between the two phenyl rings is 55.98 (15)°.

The the molecular packing in the solid state is stabilized by a C–H···S type intermolecular hydrogen bonding interactions and a C—H···π interaction between a benzene H atom and the phenyl ring of neighbouring molecules, with a C5—H5···Cg1ⁱⁱ separation of 2.70 Å [Table 2; Cg1 is the C12—C17 phenyl ring, symmetry code: (ii) -x + 1/2, y - 1/2, z - 1/2].

Experimental

All experiments were performed under argon using freshly distilled dry solvents. CS₂(0.1 ml, 1.60 mmol) was added to a solution of bis[1,3-di(3-phenylpropyl)benzimidazolidine-2-ylidene] (0.55 g, 0.78 mmol) (Yılmaz, 2008) in toluene (5 ml). A red precipitate formed instantly. The red compound was washed twice with Et₂O and crystallized from EtOH. [Yield: 0.60 g, 90%; m.p: 383–384 ° K]. Analysis calculated for C₂₆H₂₆N₂S₂: C 72.56, H 6.05, N 6.05, S 14.88%; found: C 71.99, H 5.93, N 6.30, S 14.18%.