Methyl 3-(2-hy­droxy­benzyl­idene)-2-methyl­dithio­carbazate

S K S Hazari; Sebastian Suarez; Biplab Ganguly; Fabio Doctorovich; Tapashi G Roy

doi:10.1107/S160053681201731X

. 2012 Apr 25;68(Pt 5):o1533. doi: 10.1107/S160053681201731X

Methyl 3-(2-hydroxybenzylidene)-2-methyldithiocarbazate

S K S Hazari ^a, Sebastian Suarez ^b, Biplab Ganguly ^a, Fabio Doctorovich ^b, Tapashi G Roy ^a,^*

PMCID: PMC3344635 PMID: 22590397

Abstract

In the title compound, C₁₀H₁₂N₂OS₂, the thione and S-methyl groups are syn. An intramolecular bifurcated O—H⋯(S,N) hydrogen bond occurs.

Related literature

For the biological activity of sulfur-ligand compounds, see: French & Blang (1965 ▶); Ali & Livingstone (1974 ▶); Ali et al. (1995 ▶); Hazari et al. (1999 ▶, 2002 ▶). For the synthesis and characterization of sulfur–nitrogen-containing ligands, see: Hazari et al. (2002 ▶, 2006 ▶). For a related structure, see: Hazari et al. (2012 ▶).

Experimental

Crystal data

C₁₀H₁₂N₂OS₂
M _r = 240.34
Monoclinic,
a = 11.3561 (16) Å
b = 8.9033 (13) Å
c = 11.5045 (16) Å
β = 91.411 (13)°
V = 1162.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 298 K
0.35 × 0.30 × 0.22 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.859, T _max = 0.917
16680 measured reflections
2833 independent reflections
2039 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.171
S = 1.05
2833 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681201731X/qm2064sup1.cif

e-68-o1533-sup1.cif^{(14KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201731X/qm2064Isup2.hkl

e-68-o1533-Isup2.hkl^{(136.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681201731X/qm2064Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯S2	0.91 (5)	2.67 (5)	3.453 (2)	145 (4)
O1—H1O⋯N1	0.91 (5)	1.88 (5)	2.678 (3)	145 (4)

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Acknowledgments

The authors acknowledge the UGC, Bangladesh, for the award of a fellowship to BG and thank the TWAS, Trieste, Italy, for awarding a TWAS–UNESCO Associateship to TGR. They are also grateful to ANPCyT for a grant (PME–2006– 01113) and to R. Baggio for his helpful suggestions.

supplementary crystallographic information

Comment

It is well known that sulfur-containing compounds have potential biological activities (French & Blang, 1965; Ali & Livingstone, 1974; Ali et al., 1995; Hazari et al., 1999; Hazari et al., 2002). As a continuation of the synthesis and characterization of sulfur-nitrogen containing ligands (Hazari et al., 1999; Hazari et al., 2002) and their metal complexes, the present investigation is an attempt to prepare a complex of vanadium(IV) with the Schiff base ligand (L, prepared by the condensation of salicylaldehyde and N-methyl-S– methyldithiocarbamate). Although a greenish yellow complex was obtained, during crystallization from ethanol, the ligand (m.p. 126–128°C) was regenerated in the form of a crystal. Hence, the crystal structure of the ligand has been described.

In the crystal structure of (1) (Fig.1), there is a bifurcated hydrogen bond involving O1 - H10 ··· S2 and O1 - H10 ··· N1 interactions. The O1 S2 and O1 N1 distances are 3.453 (2) Å and 2.678 (3) Å respectively.

Experimental

The title compound was isolated by following four steps synthetic procedure:

Step1. Synthesis of N-methyl-S-methyldithiocarbamate: Potassium hydroxide (11.5 g) was dissolved in 60 ml of 90% ethanol and the mixture was cooled down to 273 K in an ice bath. To this, methylhydrazine (11.1 ml) was added slowly with mechanical stirring. A solution of carbondisulfide (12 ml) was added dropwise from a burette with constant stirring over a period of an hour. During the addition of carbondisulfide, the temperature of the reaction mixture was not allowed to rise above 279 K. A yellow colored solution was obtained. After adding carbondisulfide, methyl iodide (12.5 ml) was added from a burette dropwise with vigorous mechanical stirring. After the complete addition, the mixture was stirred for further 15 minutes, whereupon well formed shining crystals appeared. The product was separated by filtration and washed with water and recrystallized from ethanol and dried in a vacuum desiccator over silica gel. Yield: 15.25 g, M.pt.: 361–363 K.

Step 2. Synthesis of methyl-N-(2-hydroxybenzyledine)-N-methyl hydrazinecarbodithionate, L (1): A hot solution of salicyladehyde (1.04 ml, 10 mmol) in absolute ethanol (40 ml) was mixed with hot solution of N-methyl-S– methyldithiocarbamate (1.36 g, 10 mmol) in the same solvent. The mixture was refluxed for 6 h. on a water bath. After reducing the volume, a yellowish white product appeared which was filtered off. This product was washed with ethanol several times (3 x 2 ml) and dried in a vacuum desiccator over silica gel. Yield: 1.65 g. M.pt.: 399–401 K.

Step 3. Attempted preparation of the oxovanadium(IV) complex with (I): Vanadyl acetylacetonate [VO2(acac)2] (2.65 g, 10 mmol) was dissolved in dry ethanol, in which a hot solution of L (2.4 g, 10 mmol) in dry ethanol was added. The mixture was refluxed for 6 h. on water bath. After reducing the volume and standing over night a light greenish yellow product appeared, which was washed with ethanol for several times and dried in a vacuum desiccator over silica gel. Melting point of product was 443–445 K.

Step 4. Crystallization: The product was dissolved in ethanol to which half volume of petroleum ether was added (10/5 ml v/v). The solution was left for several days after which the title compound, (I), was deposited as crystals.