1-Tosyl-2-[(1-tosyl-1H-benzimidazol-2-yl)methyl­sulfanyl]-1H-benzimidazole

Nassir N Al-Mohammed; Yatimah Alias; Zanariah Abdullah; Hamid Khaledi

doi:10.1107/S1600536811011822

. 2011 Apr 7;67(Pt 5):o1043. doi: 10.1107/S1600536811011822

1-Tosyl-2-[(1-tosyl-1H-benzimidazol-2-yl)methylsulfanyl]-1H-benzimidazole

Nassir N Al-Mohammed ^a,^‡, Yatimah Alias ^a, Zanariah Abdullah ^a, Hamid Khaledi ^a,^*

PMCID: PMC3089064 PMID: 21754370

Abstract

In the title compound, C₂₉H₂₄N₄O₄S₃, the two N-tosylbenzimidazolyl unit are connected through a —S—CH₂— fragment, the dihedral angle between the benzimidazole rings being 76.09 (5)°. The methylthio group is disordered with respect to exchange of the S and C atoms in a 0.547 (4):0.453 (4) ratio. In the crystal, C—H⋯O and C—H⋯π interactions connect adjacent molecules into infinite layers parallel to the ab plane. The crystal packing is further stabilized by a π–π interaction [centroid–centroid separation = 3.5187 (4) Å].

Related literature

For the structures of similar compounds, see: Hayashi et al. (2008 ▶); Rashid et al. (2006 ▶, 2007 ▶).

Experimental

Crystal data

C₂₉H₂₄N₄O₄S₃
M _r = 588.70
Triclinic,
a = 8.2524 (6) Å
b = 13.5905 (10) Å
c = 13.8117 (10) Å
α = 62.5191 (8)°
β = 75.4090 (9)°
γ = 85.9930 (9)°
V = 1327.99 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 100 K
0.38 × 0.35 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.887, T _max = 0.935
8528 measured reflections
4762 independent reflections
4405 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.117
S = 1.05
4762 reflections
382 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011822/pv2404sup1.cif

e-67-o1043-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011822/pv2404Isup2.hkl

e-67-o1043-Isup2.hkl^{(233.2KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C8–C13 and C23–C28 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O4ⁱ	0.95	2.48	3.314 (3)	147
C20—H20⋯O3ⁱⁱ	0.95	2.46	3.386 (3)	164
C25—H25⋯Cg1ⁱⁱⁱ	0.95	2.99	3.744 (3)	138
C15—H15A⋯Cg2^iv	0.99	2.98	3.62 (2)	124

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

Acknowledgments

The authors thank the University of Malaya for funding this study (FRGS grant No. FP001/2010 A).

supplementary crystallographic information

Comment

The title compound (Fig. 1) is the N-tosylation product of 2-(thiomethyl-2'-benzimidazolyl)-benzimidazole. The two benzimidazolyl rings are connected through the methythio fragment, making a dihedral angle of 76.09 (5)°. The two N-bound tosyl groups and the benzimidazolyl rings subtend angles of 103.77 (10)° at S1 and 104.48 (10)° at S3 atoms. These values are comparable to those reported for similar structures (Hayashi et al., 2008; Rashid et al., 2006; Rashid et al., 2007). In the crystal, intermolecular C—H···O and C—H···π interactions link the adjacent molecules into polymeric layers parallel to the ab plane. The crystal packing is further stabilized by a π—π interaction formed by the six-membered rings (C8—C13) of anti-parallelly arranged benzimidazole rings related by symmetry of -x, -y, -z + 1 [centroids separation = 3.5187 (4) Å]. Moreover, intramolecular C—H···O and C—H···N hydrogen bonding occurs (Table 1).

Experimental

Sodium (0.17 g) was added to a solution of 2-mercaptobenzimidazole (1 g, 6.7 mmol) in anhydrous methanol (20 ml) and the mixture was stirred at room temperature for 20 minutes. To the mixture, 2-chloromethylbenzimidazole (1.11 g, 6.67 mmol) was added dropwise under vigorous stirring, and then left to stir overnight. The solvent was removed under reduced pressure and the remaining liquid was washed with water and crystallized from tetrahydrofuran (THF) to give the white solid of 2-(thiomethyl-2'-benzimidazolyl)-benzimidazole. A solution of p-toluene sulfonyl chloride (0.75 g, 3.91 mmol) in pyridine (5 ml) was added dropwise to a solution of 2-(thiomethyl-2'-benzimidazolyl)-benzimidazole (0.5 g, 1.78 mmol) in pyridine (5 ml) at 273 K, within 2 hr. The mixture was stirred at room temperature overnight and then poured into a beaker containg 100 ml ice water. It was then stirred for another 15 minutes, extracted with dichloromethane and washed with distilled water (3 x 10 ml). The organic layer was dried with magnesium sulfate and evaporated. The obtained solid was recrystallized from toluene to give the colorless crystals of the title compound.