Benzyl 3-[(E,E)-3-phenyl­prop-2-enyl­idene]dithio­carbazate

M T H Tarafder; K A Crouse; M Toihidul Islam; Suchada Chantrapromma; Hoong-Kun Fun

doi:10.1107/S1600536808013354

. 2008 May 10;64(Pt 6):o1042–o1043. doi: 10.1107/S1600536808013354

Benzyl 3-[(E,E)-3-phenylprop-2-enylidene]dithiocarbazate

M T H Tarafder ^a,^*, K A Crouse ^b, M Toihidul Islam ^c, Suchada Chantrapromma ^d,^‡, Hoong-Kun Fun ^e,^§

PMCID: PMC2961473 PMID: 21202563

Abstract

The title compound, C₁₇H₁₆N₂S₂, a dithiocarbazate derivative, adopts an EE configuration with respect to the C=C and C=N double bonds of the propenylidine group. The 3-phenylprop-2-enylidene and dithiocarbazate fragments lie essentially in the same plane, with a maximum deviation from that plane of 0.074 (2) Å, while the dihedral angle between the 3-phenylprop-2-enylidene and the benzyl group is 77.78 (7)°. In the crystal structure, molecules are linked by an N—H⋯S hydrogen bond and a weak C—H⋯S interaction involving the terminal thione S atom, forming dimers that are arranged into sheets parallel to the bc plane. The crystal structure is also stabilized by C—H⋯π interactions.

Related literature

For information on values of bond lengths, see Allen et al. (1987 ▶). For related structures of dithiocarbazate derivatives, see, for example: Crouse et al. (2004 ▶); Fun et al. (2008 ▶); Shanmuga Sundara Raj et al. (2000 ▶). For applications and bioactivities of dithiocarbazate derivatives, see, for example: Ali & Tarafder (1977 ▶); Ali et al. (2001 ▶, 2002 ▶, 2008 ▶); Chan et al. (2008 ▶); Chew et al. (2004 ▶); Crouse et al. (2004 ▶); Tarafder et al. (1978 ▶, 1981 ▶, 2001 ▶, 2008 ▶).

Experimental

Crystal data

C₁₇H₁₆N₂S₂
M _r = 312.44
Triclinic,
a = 5.4350 (3) Å
b = 11.6333 (7) Å
c = 13.6289 (8) Å
α = 66.869 (4)°
β = 82.723 (4)°
γ = 87.520 (4)°
V = 786.04 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100.0 (1) K
0.58 × 0.19 × 0.05 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.829, T _max = 0.982
16100 measured reflections
3570 independent reflections
2870 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.092
S = 1.07
3570 reflections
194 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808013354/sj2494sup1.cif

e-64-o1042-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013354/sj2494Isup2.hkl

e-64-o1042-Isup2.hkl^{(175KB, hkl)}

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
N1—H1N1⋯S2ⁱ	0.87 (2)	2.53 (2)	3.3714 (19)	165 (2)
C9—H9A⋯S2ⁱ	0.93	2.93	3.7264 (18)	144
C15—H15A⋯Cg1ⁱⁱ	0.93	2.83	3.649 (2)	148

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C1–C6 phenyl ring.

Acknowledgments

KAC thanks Universiti Putra Malaysia for financial help. MTHT thanks the University of Rajshahi for the provision of laboratory facilities. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

There has been immense interest in nitrogen-sulfur donor ligands since our report on S-benzyldithiocarbazate (SBDTC) (Ali & Tarafder, 1977). There have also been a number of reports of Schiff bases derived from SBDTC (Ali et al., 2001, 2002, 2008; Chan et al., 2008; Chew et al., 2004; Tarafder et al., 1978, 1981, 2001; Raj et al., 2000). The intriguing coordination chemistry and increasingly important biomedical properties of ligands derived from SBDTC have also received much attention (Ali et al., 2001, 2002; Crouse et al., 2004; Tarafder et al., 2001, 2008). The synthesis and structure of SBDTC have been reported previously (Ali & Tarafder (1977); Shanmuga Sundara Raj et al., 2000). In continuation of our research, the title compound (I), a ligand with both N and S donor atoms, was synthesized and its crystal structure is reported here. (I) is likely to have biomedical properties similar to other nitrogen-sulfur donor ligands studied by our group.

In the title compound (Fig. 1), the 3-phenylprop-2-enylidene amide (N2/C9–C17) and benzyl groups (C1–C7) adopt trans and cis positions with respect to the terminal thione S2 atom about the C8-N1 and C8-S1 bonds, respectively. The 3-phenylprop-2-enylidene (C9–C17) and the dithiocarbazate (N1/N2/S1/S2/C8) fragments is essentially planar with maximum deviation 0.074 (2) Å for C11, while the dihedral angle between the 3-phenylprop-2-enylidene and the benzyl group is 77.78 (7)°. The bond lengths and angles are in normal ranges (Allen et al., 1987). However the C═S distance of 1.7466 (17) Å is longer than the typical value of dithiocarbazate derivatives (Crouse et al., 2004; Fun et al., 2008; Shanmuga Sundara Raj et al., 2000) but being intermediate between the values of 1.82 Å for a C—S single bond and 1.56 Å for a C═S double bond (Suton, 1965). The C9–N2 distance of 1.285 (2) Å indicates a double bond charactor. The bond angles S1–C8–S2 [124.67 (10)°] and N1–C8–S1 [113.76 (13)°] also agree with those observed in trans-cisS-benzyl dithiocarbazate (Shanmuga Sundara Raj et al., 2004).

In the crystal packing (Fig. 2), the molecules are linked by an N1—H1···S2ⁱ hydrogen bond (symmetry code: i = -x, 1-y, 1-z) (Table 1) and a weak C9—H9A···S2ⁱ interaction involving the terminal thione-S atom forming dimers that are arranged into sheets parallel to the bc plane. The crystal is also stabilized by C—H···π interactions (Table 1) involving the C1–C6 phenyl ring (centroid Cg1).

Experimental

The title compound was synthesized by adding cinnamaldehyde (1.34 g, 10 mmol) to a solution of S-benzyldithiocarbazate (SBDTC) (1.98 g, 10 mmol) in absolute ethanol (60 ml) and the mixture was refluxed for 40 min. The yellow precipitate, which formed was separated and dried in vacuo over anhydrous CaCl₂ (Yield: 2.1 g, 63%). Yellow needle shaped single crystals of (I) were obtained after recrystallization from absolute ethanol over 15 days; M.p 454 K.