Benzyl N-[(Z)-(1-methyl-2-sulfanyl­propyl­idene)amino]­carbamodithio­ate

Mohammed Khaled bin Break; Sachin Mehta; M Ibrahim M Tahir; Karen A Crouse; Teng-Jin Khoo

doi:10.1107/S1600536812051008

. 2013 Jan 4;69(Pt 2):o178. doi: 10.1107/S1600536812051008

Benzyl N-[(Z)-(1-methyl-2-sulfanylpropylidene)amino]carbamodithioate

Mohammed Khaled bin Break ^a, Sachin Mehta ^a, M Ibrahim M Tahir ^b, Karen A Crouse ^b, Teng-Jin Khoo ^a,^*

PMCID: PMC3569240 PMID: 23424463

Abstract

The title compound, C₁₂H₁₆N₂S₃, was obtained by the condensation reaction of S-benzyl dithiocarbazate and 3-mercaptobutan-2-one. The phenyl ring and thiol (SH) group are approximately perpendicular [S—C—C—C and N—C—C—S torsion angles = 67.8 (3) and 116.9 (2)°, respectively] to the rest of the molecule. In the crystal, molecules are linked by weak S—H⋯S and N—H⋯S hydrogen bonds, π–π interactions between the benzene rings [centroid–centroid distance = 3.823 (2) Å] and C—H⋯π interactions.

Related literature

For biological applications of Schiff base ligands and complexes derived from S-benzyldithiocarbazate, see: Hossain et al. (1996 ▶); Tarafder et al. (2002 ▶). For related structures derived from S-benzyldithiocarbazate, which exhibit a similar geometry to the title compound, see: Khoo et al. (2005 ▶); How et al. (2007 ▶); Shan et al. (2011 ▶). For the synthesis, see: Tarafder et al. (2002 ▶). graphic file with name e-69-0o178-scheme1.jpg

Experimental

Crystal data

C₁₂H₁₆N₂S₃
M _r = 284.47
Monoclinic,
a = 16.3887 (4) Å
b = 8.3136 (2) Å
c = 10.1404 (3) Å
β = 90.234 (2)°
V = 1381.61 (6) Å³
Z = 4
Cu Kα radiation
μ = 4.73 mm⁻¹
T = 100 K
0.25 × 0.10 × 0.08 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.31, T _max = 0.68
7359 measured reflections
2615 independent reflections
2374 reflections with I > 2σ(I)
R _int = 0.027
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.123
S = 0.99
2605 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(15.7KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812051008/nk2192sup1.cif

e-69-0o178-sup1.cif^{(15.7KB, cif)}

Click here for additional data file.^{(164.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051008/nk2192Isup2.hkl

e-69-0o178-Isup2.hkl^{(164.3KB, hkl)}

Click here for additional data file.^{(3.4KB, mol)}

Supplementary material file. DOI: 10.1107/S1600536812051008/nk2192Isup3.mol

Click here for additional data file.^{(4.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812051008/nk2192Isup4.cml

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

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

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
S15—H151⋯S3ⁱ	1.38	2.96	4.186 (1)	146
N11—H111⋯S1ⁱⁱ	0.86	2.72	3.567 (2)	168
C7—H71⋯Cg ⁱⁱⁱ	0.95	2.97	3.827 (3)	152

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

Acknowledgments

The authors thank the Ministry of Higher Education Malaysia (MOHE) under FRGS (F0010.54.02) for providing a grant for this study.

supplementary crystallographic information

Comment

The past few years have seen a growing interest in the synthesis of Schiff base ligands and metal complexes specifically those derived from dithiocarbazates (Tarafder et al., 2002; Hossain et al., 1996). S-benzyldithiocarbazate (SBDTC) has been extensively studied due to the possibility of modifying its derivatives by the introduction of different substituents (Khoo et al., 2005), furthermore, SBDTC-derived Schiff base ligands have been shown to possess antimicrobial and anticancer properties (Hossain et al., 1996). Therefore, we have managed to synthesize the title compound, (I), which was a result of the condensation reaction between SBDTC and 3-mercaptobutan-2-one in order to investigate the bioactivity of this ligand and its metal complexes. In our course of research we have managed to grow crystals of the title compound, (I), from ethanol via the slow evaporation method.

X-ray crystallographic analysis has shown that the molecule [Fig.1] is planar with the phenyl ring and thiol group being nearly perpendicular to the rest of the molecule [S3—C4—C5—C10 and N12—C13—C14—S15 torsion angles of 67.8 (3)° and 116.9 (2)°, respectively]. The bond C2—N11 has a length of 1.3503 (3) Å whereas C13—N12 has a bond length of 1.278 (3) Å which is shorter than the former indicating that the latter possesses a double-bond character and belongs to the imine group. Similarly, the C2—S1 bond has a length of 1.659 (3) Å which is the shortest bond length relative to the other C—S bonds, and that indicates that it possesses a double bond character which further proves that the ligand exists in the thione tautomer in solid state. The bond lengths of the imine group (C=N) and that of the thione group (C=S) are similar to those reported in previously synthesized dithiocarbazate compounds [1.289 (3) Å for C=N, 1.664 (2) Å for C=S; Khoo et al., 2005] and [1.285 (2) Å for C=N, 1.6667 (15) Å for C=S; Tarafder et al., 2002], which indicates that such bond lengths are typical of Schiff base ligands derived from dithiocarbazates. The molecules in the crystal are linked together via intermolecular H···S [Fig.2] hydrogen bond interactions (Table 2). The benzene rings at (x, y, z) and (1 - x, 2 - y, 1 - z) are stacked parallel to each other and form π- π interactions with a separation of 3.823 Å and a shift distance of 1.539 Å [Fig.3.], while the distance between the planes of the benzene rings is 3.500 Å. Furthermore, there are C—H···π interactions (Table 2) between the molecules of the structure [Fig.4.] and the perpendicular distance between the plane of the benzene ring and H71 was found to be 2.790 Å. Cg in (Table 2) refers to the centroid of the benzene ring present in the structure.

The molecule crystallizes in the conformer in which the thione sulfur is in a trans position with the ketone moiety across the C2—N11 bond but adopts a cis position with the phenyl group across the C2—S3 bond. The ketone moiety is cis to the phenyl group with respect to the C2—N11 bond. Such geometrical arrangements are similar to dithiocarbazate derived compounds reported previously (Khoo et al., 2005; How et al., 2007).

Experimental

The method used for synthesis of the Schiff base ligand was a modified form of the one reported by (Tarafder et al., 2002). (0.02) moles of S-benzyldithiocarbazate were dissolved in 40 ml absolute ethanol and then heated on a heating plate with constant stirring in order to ensure complete dissolving. Similarly, (0.02) moles of 3-mercaptobutan-2-one were mixed with 40 ml of absolute ethanol and heated on a heating plate for 10 minutes. The reactants were mixed and 2–4 drops of concentrated H₂SO₄ were added to the mixture. The mixture was kept on the heating plate for 5 more minutes and then cooled to 0°C in an ice-bath until the Schiff base precipitated. The Schiff base precipitated was filtered via suction filtration, washed with cold ethanol and dried over silica gel (yield 79.7%, m.p 361.45 K). Crystals suitable for X-ray analysis have been obtained via slow evaporation of ethanol over a period of 10 days.