Crystal structure of S-hexyl (E)-3-(4-methyl­benzyl­idene)di­thio­carbazate

M B H Howlader; M S Begum; M C Sheikh; R Miyatake; E Zangrando

doi:10.1107/S2056989015000080

. 2015 Jan 10;71(Pt 2):o103–o104. doi: 10.1107/S2056989015000080

Crystal structure of S-hexyl (E)-3-(4-methylbenzylidene)dithiocarbazate

M B H Howlader ^a, M S Begum ^a,^*, M C Sheikh ^b, R Miyatake ^c, E Zangrando ^d

PMCID: PMC4384598 PMID: 25878852

Abstract

In the title compound, C₁₅H₂₂N₂S₂, the dithiocarbazate group adopts an E conformation with respect to the C=N bond of the benzylidene moiety. In the crystal, molecules are linked by pairs of N—H⋯S hydrogen bonds, forming inversion dimers with an R ² ₂(8) ring motif. The dimers are linked via C—H⋯π interactions, forming chains propagating along [100].

Keywords: crystal structure, S-hexyl dithiocarbazate, bidentate Schiff base, N—H⋯S hydrogen bonds, C—H⋯π interactions.

Related literature

For the biological properties of bidentate Schiff bases of S-methyl dithiocarbazate or S-benzyl dithiocarbazate and their bivalent metal complexes, see: Chan et al. (2008 ▸); How et al. (2008 ▸); Tarafder et al. (2002 ▸); Ali et al. (2002 ▸); Chew et al. (2004 ▸); Crouse et al. (2004 ▸). For their N,S-chelating behavior towards metal atoms, see for example: Islam et al. (2011 ▸). For the structures of related compounds, see: Tarafder et al. (2008 ▸, 2010 ▸).

Experimental

Crystal data

C₁₅H₂₂N₂S₂
M _r = 294.47
Triclinic,
a = 4.79244 (9) Å
b = 11.3790 (2) Å
c = 14.5382 (3) Å
α = 100.1666 (7)°
β = 91.2117 (7)°
γ = 94.6754 (7)°
V = 777.26 (3) Å³
Z = 2
Cu Kα radiation
μ = 3.00 mm⁻¹
T = 173 K
0.19 × 0.11 × 0.07 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 2001 ▸) T _min = 0.615, T _max = 0.811
8970 measured reflections
2802 independent reflections
2162 reflections with F ² > 2.0σ(F ²)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.129
S = 1.04
2802 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2001 ▸); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: CrystalStructure (Rigaku, 2010 ▸); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S2056989015000080/su5050sup1.cif

e-71-0o103-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000080/su5050Isup2.hkl

e-71-0o103-Isup2.hkl^{(137.5KB, hkl)}

Click here for additional data file.^{(6KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015000080/su5050Isup3.cml

Click here for additional data file.^{(27.4KB, tif)}

. DOI: 10.1107/S2056989015000080/su5050fig1.tif

A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.1MB, tif)}

a . DOI: 10.1107/S2056989015000080/su5050fig2.tif

A partial view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

CCDC reference: 1035819

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C1C6 ring.

DHA	DH	HA	D A	DHA
N2H9S1ⁱ	0.83(3)	2.56(3)	3.3760(19)	168(2)
C1H2Cg1ⁱⁱ	0.98	2.61	3.529(3)	157

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

Acknowledgments

MBHH and MSB are grateful to the Department of Chemistry, Rajshahi University, for the provision of laboratory facilities. MCS acknowledges the Department of Applied Chemistry, Toyama University, for providing funds for single-crystal X-ray analyses.

supplementary crystallographic information

S1. Synthesis and crystallization

To an ethanolic solution of KOH (2.81 g, 0.05 mol) hydrazine hydrate (2.50 g, 0.05 mol, 99%) was added and the mixture was stirred at 273 K. To this solution carbon disulfide (3.81 g, 0.05 mol) was added drop wise with constant stirring for one hour. Then n-bromohexane (8.25 g, 0.05 mol) was added drop wise with vigorous stirring at 273 K for an additional hour. Finally, 4-methylbenzaldehyde (6.0 g, 0.05 mol) in ethanol was added and the mixture refluxed for 30 min. The mixture was filtered while hot and then the filtrate was cooled to 273 K giving a precipitate of the Schiff base product. It was recrystallized from ethanol at room temperature and dried in a vacuum desiccator over anhydrous CaCl₂. Colourless crystals, suitable for X-ray diffraction, of the title compound were obtained by slow evaporation of a solution in ethanol/acetonitrile (2:1) after 23 days (m.p.: 357 K).

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atom of the NH group was located in a difference Fourier map and freely refined. The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95–0.99 Å with U_iso(H) = 1.5U_eq(C) for methy H atoms and = 1.2U_eq(C) for other H atoms.

S3. Comment

Bidentate Schiff bases of S-methyl dithiocarbazate or S-benzyl dithiocarbazates and their bivalent metal complexes have received considerable attention in the field of medical science for their antibacterial, antifungal, antiviral, antitumour, and anticancer activities (Chan et al., 2008; How et al., 2008; Tarafder et al., 2002; Ali et al., 2002; Chew et al., 2004; Crouse et al., 2004)

The molecular structure of the title compound is shown in Fig. 1. The Schiff base exists in the thione tautomeric form with the dithiocarbazate fragment adopting an E conformation with respect to the C═N bond of the benzylidene moiety. The β-nitrogen and the thioketo sulphur are trans located with respect to the C9—N2 bond. The bond lengths and angles are within the normal ranges and are comparable to those in related structures (Tarafder et al., 2008, 2010). The molecule is in its thione tautomeric and the co-planarity of atoms (with the exception of the S-hexyl chain) indicates an electron delocalization within it. The molecule, when used in coordination chemistry, requires a rotation about the C9—N2 by 180 ° in order to allow the N,S chelating behavior towards the metal atom (Islam et al., 2011).

In the crystal, molecules are linked by pairs of N—H···S hydrogen bonds forming inversion dimers with an R²₂(8) ring motif (Table 1 and Fig. 2). The dimers are linked via C—H···π interactions forming chains propagating along the a axis direction (Table 1).