1-Methyl-2-({[(2-methyl­phen­yl)meth­yl]disulfan­yl}meth­yl)benzene

Shahedeh Tayamon; Thahira Begum S A Ravoof; Mohamed Ibrahim Mohamed Tahir; Karen A Crouse; Edward R T Tiekink

doi:10.1107/S160053681202418X

. 2012 May 31;68(Pt 6):o1953. doi: 10.1107/S160053681202418X

1-Methyl-2-({[(2-methylphenyl)methyl]disulfanyl}methyl)benzene

Shahedeh Tayamon ^a, Thahira Begum S A Ravoof ^a, Mohamed Ibrahim Mohamed Tahir ^a, Karen A Crouse ^a,^‡, Edward R T Tiekink ^b,^*

PMCID: PMC3379504 PMID: 22719702

Abstract

In the title disulfide, C₁₆H₁₈S₂, the molecule is twisted about the central S—S bond [the C—S—S—C torsion angle = 93.24 (7)°] and the dihedral angle between the benzene rings is 72.84 (7)°, indicating an almost orthogonal relationship; the methyl groups are orientated to the same side of the molecule. The crystal packing features C—H⋯.π interactions which consolidate a three-dimensional architecture.

Related literature

For background to the coordination chemistry of dithiocarbazate derivatives, see: Crouse et al. (2004 ▶); Ravoof et al. (2010 ▶). For the synthesis and methodology, see: Tarafder et al. (2000 ▶). For the structure of bis(benzyl)disulfide, see: van Dijk & Visser (1971 ▶). graphic file with name e-68-o1953-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₈S₂
M _r = 274.42
Monoclinic,
a = 10.3640 (4) Å
b = 7.6408 (3) Å
c = 18.1106 (7) Å
β = 91.099 (3)°
V = 1433.90 (10) Å³
Z = 4
Cu Kα radiation
μ = 3.18 mm⁻¹
T = 100 K
0.56 × 0.38 × 0.21 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.299, T _max = 0.513
9993 measured reflections
2773 independent reflections
2672 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.096
S = 1.06
2773 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681202418X/hb6818sup1.cif

e-68-o1953-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202418X/hb6818Isup2.hkl

e-68-o1953-Isup2.hkl^{(133.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681202418X/hb6818Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C2–C7 and C10–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯Cg1ⁱ	0.99	2.91	3.4605 (16)	116
C16—H16B⋯Cg2ⁱⁱ	0.98	2.85	3.7392 (18)	151
C16—H16C⋯Cg1ⁱⁱⁱ	0.98	2.97	3.7764 (18)	140

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

Acknowledgments

Support for the project came from Universiti Putra Malaysia (UPM) through the purchase of the diffractometer and under their Research University Grant Scheme (RUGS No. 9174000), the Malaysian Ministry of Science, Technology and Innovation (grant No. 09-02-04-0752-EA001) and the Malaysian Fundamental Research Grant Scheme (FRGS No. 01-13-11-986FR). The authors also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

Our interest in investigating the coordination properties of ligands containing the H—N—C═S moiety and our desire to expand the study of this class of biologically important compounds has lead us to synthesize series of related ligands (Tarafder et al., 2000; Crouse et al., 2004; Ravoof et al., 2010). The title compound, [(2-methyl)benzyl]disulfide, (I), was obtained during the attempt to prepare the phenyl hydrazine analogue of S-benzyldithiocarbazate.

In (I), Fig. 1, the molecule is twisted about the central S1—S2 bond as seen in the value of the C1—S1—S2—C9 torsion angle of 93.24 (7) Å. The dihedral between the benzene rings is 72.84 (7)°, indicating an almost orthogonal relationship, and the methyl groups are orientated to the same side of the molecule. The overall conformation in (I) contrasts that found in the parent compound, bis(benzyl)disulfide (van Dijk & Visser, 1971), which adopts an open conformation with both phenyl rings directed away from the sulfur atoms. In (I), the S1-bound benzyl is directed away having an anti disposition [the S2—S1—C1—C2 torsion angle is 176.23 (9)°] whereas the S2-bound benzyl residue in bis(benzyl)disulfide (van Dijk & Visser, 1971) has a syn conformation [S1—C1—C2—C7 = 91.90 (14)°].

The crystal packing is dominated by C—H···.π interactions, Table 1, which consolidates a three-dimensional architecture, Fig. 2.

Experimental

[(2-Methyl)benzyl]disulfide was isolated as a by-product from the synthesis of the phenylhydrazine analog of S-benzyldithiocarbazate (Tarafder et al., 2000). Potassium hydroxide (0.2 mol, 11.2 g) was completely dissolved in absolute ethanol (70 ml) and phenylhydrazine (0.2 mol, 21.6 g) was added to the solution cooled in an ice-salt bath producing a dark-yellow solution. Carbon disulfide (0.2 mol, 15.2 g) was added drop-wise with constant stirring over one hour. 2-Methylbenzyl chloride (0.1 mol, 13.2 ml) was then added drop-wise with vigorous stirring. The temperature of reaction was maintained below 278 K. The high yield yellow-white product was filtered and dried in a dessicator over anhydrous silica gel, dissolved in absolute ethanol and kept in a freezer. A few colourless blocks were harvested on the third day and washed with cold n-hexane.