Crystal structure of S-octyl (E)-3-(4-meth­oxy­benzyl­idene)di­thio­carbazate

M S Begum; E Zangrando; M C Sheikh; R Miyatake; M M Hossain

doi:10.1107/S205698901500568X

. 2015 Mar 28;71(Pt 4):o265–o266. doi: 10.1107/S205698901500568X

Crystal structure of S-octyl (E)-3-(4-methoxybenzylidene)dithiocarbazate

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

PMCID: PMC4438792 PMID: 26029448

Abstract

As already observed in similar molecules, the dithiocarbazate group in the title compound, C₁₇H₂₆N₂OS₂, adopts an EE configuration with respect to the C=N bond of the benzylidene moiety. In the crystal, molecules are connected into inversion dimers by pairs of N—H⋯S hydrogen bonds. The dimers are linked by weak π–π interactions, with centroid-to-centroid distances of 3.723 (11) Å, forming chains parallel to [110].

Keywords: crystal structure, dithiocarbazate, S-containing Schiff bases, hydrogen bonding

Related literature

For the structures of related compounds, see: Howlader et al. (2015 ▸); Begum et al. (2015 ▸). For metal complexes containing similar ligands, 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 ▸).

Experimental

Crystal data

C₁₇H₂₆N₂OS₂
M _r = 338.53
Monoclinic,
a = 28.7970 (6) Å
b = 8.37150 (15) Å
c = 15.6207 (3) Å
β = 104.2210 (7)°
V = 3650.36 (12) Å³
Z = 8
Cu Kα radiation
μ = 2.66 mm⁻¹
T = 173 K
0.32 × 0.21 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ▸) T _min = 0.581, T _max = 0.708
20438 measured reflections
3333 independent reflections
3140 reflections with F ² > 2σ(F ²)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.096
S = 1.06
3333 reflections
205 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.33 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/S205698901500568X/rz5151sup1.cif

e-71-0o265-sup1.cif^{(32.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500568X/rz5151Isup2.hkl

e-71-0o265-Isup2.hkl^{(163.6KB, hkl)}

Click here for additional data file.^{(6.8KB, cml)}

Supporting information file. DOI: 10.1107/S205698901500568X/rz5151Isup3.cml

Click here for additional data file.^{(34.5KB, tif)}

. DOI: 10.1107/S205698901500568X/rz5151fig1.tif

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

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

. DOI: 10.1107/S205698901500568X/rz5151fig2.tif

Crystal packing of the title compound showing pairs of molecules connected by N—H⋯S hydrogen interactions (dashed lines). H atoms not involved in hydrogen bonding are omitted.

CCDC reference: 1044476

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H9S1ⁱ	0.86(2)	2.536(18)	3.3870(11)	170.9(16)

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Symmetry code: (i) Inline graphic .

Acknowledgments

MMH 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. Chemical context

Bidentate Schiff bases of S-methyl or S-benzyl dithiocarbazates and their metal complexes have received considerable attention for their possible bioactivities (Chan et al., 2008; How et al., 2008; Tarafder et al., 2002; Ali et al., 2002; Chew et al., 2004; Crouse et al., 2004). As part of our ongoing structural studies of S-containing Schiff bases (Howlader et al., 2015; Begum et al., 2015), we report herein the structure of the title compound having a long alkyl chain.

S2. Structural commentary

The molecule of the title compound is shown in Fig. 1. The Schiff base exists in thione tautomeric form with the dithiocarbazate fragment adopting an EE configuration 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. With the exception of the S-octyl chain, the atoms of the 3-(4-methoxybenzylidene)dithiocarbazate group are approximately co-planar (r.m.s. deviation = 0.253 Å) indicating electron delocalization within it. The bond lengths and angles are closely comparable to those detected in S-hexyl (E)-3-(4-methylbenzylidene)dithiocarbazate (Howlader et al., 2015) and in the S-hexyl analogue (Begum et al., 2015), characterized by a shorter alkyl chain.

S3. Supramolecular features

The crystal packing of the title compound evidences molecules connected into centrosymmetric dimers (Fig. 2) by pairs of N—H···S hydrogen bonds (Table 1), which are further linked by weak π-π stacking interactions (centroid-to-centroid distances of 3.723 (11) Å) to form chains parallel to the [1 1 0] direction.

S4. Database survey

The octyl chain shows the typical all-anti conformation with a S(2)—C(10)—C(11)—C(12) torsion angle of 169.73 (9)°, which differs from that of 66.6 (2)° measured in the corresponding S-hexyl (E)-3-(4-methylbenzylidene)dithiocarbazate (Howlader et al., 2015), but comparable to the value of 173.99 (13)° found in the hexyl derivative (Begum et al., 2015) .

S5. 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 dropwise with constant stirring for one hour. Then 1-bromooctane (9.65 g, 0.05 mol) was added dropwise with vigorous stirring at 273 K for an additional hour. Finally, 4-methoxybenzaldehyde (6.81 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, which 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 compound were obtained by slow evaporation of an ethanol/acetonitrile (2:1 v/v) solution after 19 days (m. p. 355 K).

S6. Refinement

Hydrogen atoms were located geometrically and treated as riding atoms with C—H = 0.98–0.99 Å and U_ĩso(H) = 1.2U_eq(C). The hydrogen atom at N2 was located on the difference Fourier map and freely refined.