Bis[benzyl N′-(3-phenyl­prop-2-enyl­idene)hydrazinecarbodithio­ato-κ2 N′,S]zinc(II)

Hoong-Kun Fun; Suchada Chantrapromma; M T H Tarafder; M Toihidul Islam; C M Zakaria; M A A A A Islam

doi:10.1107/S1600536808005643

. 2008 Mar 5;64(Pt 4):m518–m519. doi: 10.1107/S1600536808005643

Bis[benzyl N′-(3-phenylprop-2-enylidene)hydrazinecarbodithioato-κ² N′,S]zinc(II)

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

PMCID: PMC2961027 PMID: 21201987

Abstract

In the title Zn^II complex, [Zn(C₁₇H₁₅N₂S₂)₂], the Zn^II atom lies on a twofold rotation axis. It exists in a tetrahedral geometry, chelated by two deprotonated Schiff base ligands. The dihedral angle between each ligand is 71.48 (8)°. Molecules are connected by weak C—H⋯S intermolecular interactions into chains along the c axis. The crystal structure is further stabilized by C—H⋯π interactions involving the phenyl ring of the 3-phenylprop-2-enylidene unit.

Related literature

For the synthesis and structure of S-benzyldithiocarbazates, see: Ali & Tarafder (1977 ▶); Shanmuga Sundara Raj et al. (2000 ▶). For the structures of Zn^II complexes, see: Latheef et al. (2007 ▶); Tarafder, Chew et al. (2002 ▶). For the structures of other metal dithiocarbazates, see: Ali et al. (2001 ▶, 2002 ▶, 2008 ▶); Chew et al. (2004 ▶); Crouse et al. (2004 ▶); Tarafder et al. (2001 ▶, 2008 ▶); Tarafder, Chew et al. (2002 ▶); Tarafder, Jin et al. (2002 ▶). For the bioactivity of metal S-benzyldithiocarbazates, see, for example: Ali et al. (2001 ▶, 2002 ▶); Tarafder et al. (2001 ▶); Tarafder, Jin et al. (2002 ▶).

Experimental

Crystal data

[Zn(C₁₇H₁₅N₂S₂)₂]
M _r = 688.23
Orthorhombic,
a = 36.0897 (4) Å
b = 9.9310 (1) Å
c = 8.7633 (1) Å
V = 3140.83 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 100.0 (1) K
0.37 × 0.25 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.692, T _max = 0.841
82655 measured reflections
4580 independent reflections
4071 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.091
S = 1.15
4580 reflections
195 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.32 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/S1600536808005643/ng2427sup1.cif

e-64-0m518-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005643/ng2427Isup2.hkl

e-64-0m518-Isup2.hkl^{(224.5KB, 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
C13—H13A⋯S2ⁱ	0.93	2.76	3.6697 (17)	167
C11—H11B⋯Cg1ⁱⁱ	0.97	2.98	3.5785 (17)	121

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

Acknowledgments

MTHT and MTI thank Rajshahi University for financial support. SC thanks Prince of Songkla University for generous support. The authors also thank the Malaysian Government and Universiti Sains Malaysia for the Scientific Advancement Grant Allocation (SAGA) grant No. 304/PFIZIK/653003/A118.

supplementary crystallographic information

Comment

The coordination chemistry of the ligands derived from S-benzyldithiocarbazate (SBDTC) had been of immense interests because of their intriguing coordination chemistry as well as their increasingly important biomedical properties (Ali et al., 2001; 2002; Tarafder et al., 2001; Tarafder, Jin et al., 2002b). Synthesis (Ali & Tarafder, 1977) and structure (Shanmuga Sundara Raj et al., 2000) of SBDTC were reported. We have previously reported the Schiff bases complexes derived from dithiocarbazate derivatives (Ali et al., 2001; 2002; 2008; Chew et al., 2004; Crouse et al., 2004; Tarafder et al., 2001, 2008; Tarafder, Chew et al., 2002; Tarafder, Jin et al., 2002). In continuation of our interests, we report herein the X-ray structure of the zinc(II) complex of Schiff base ligand of SBDTC which is found to be isostructural with the copper(II) analog (Tarafder et al., 2008).

The Zn^II atom of the title complex, lies on a twofold rotation axis and therefore the asymmetric unit contains one-half of a molecule (Fig. 1). The ligands coordinate to the Zn^II through the two azomethine nitrogen and the two thiolate sulfur atoms forming a distorted tetrahedral geometry (Fig. 1). Both the two nitrogen atoms (N1 and N1A) and two sulfur atoms (S1 and S1A) from the two ligands are coordinated at opposite positions. The NS chelation results in the two five membered Zn^II-bidentate rings (Zn1, N1, N2, C8, S1), atom Zn1 having a maximum deviation of 0.0839 (5) Å. The dihedral angle between these Zn^II-bidentate rings is 80.03 (4) °. The smaller angle around Zn^II is 86.96 (3) ° for N1—Zn1—S1. The N—Zn—N and S—Zn—S bond angles are 104.32 (7) ° and 134.49 (2) °, respectively. The Zn1—N1 distance of 2.0662 (12) Å is slightly longer compared to the [Zn(C₁₄H₁₈N₃OS)₂] by Latheef et al., 2007 (Zn—N = 2.026 (3) and 2.040 (3) Å) whereas the Zn1—S1 distance of 2.2636 (4) Å in the title complex is in the same range (Zn—S = 2.2597 (13) and 2.2462 (12) Å (Latheef et al., 2007)). The mean plane of the prop-2-enylidene moiety (C7/C8/C9/N1/N2) makes a dihedral angle of 12.25 (12)° with mean plane of the attached C1–C6 phenyl ring. Atoms N1, N2, C10, S1 and S2 lie on the same plane and this plane makes a dihedral angle of 76.75 (6) ° with the C12–C17 phenyl ring. The dihedral angle between the two phenhyl rings (C1–C6 and C12–C17) is 71.48 (8)°. Bond lengths and angles observed in the Schiff base ligand are of normal values.

In the crystal packing (Fig. 2), the molecules are interconnected by weak C—H···S intermolecular interactions (Table 1) into chains along the c axis. The crystal is further stabilized by C—H···π interactions (Table 1) involving the C1–C6 phenyl ring (centroid Cg₁) of the 3-phenylprop-2-enylidene moiety.

Experimental

The Schiff base ligand was prepared following the literature procedure (Tarafder et al., 2008) by adding cinamaldehyde (1.32 g, 10 mmol) to a hot solution of S-benzyldithiocarbazate (SBDTC) (1.98 g, 10 mmol) in absolute ethanol (40 ml). The mixture was refluxed for 10 min. The yellow precipitate, which formed, was isolated and washed with hot ethanol. The yellow solid was recrystallized from absolute ethanol (Yield: 1.52 g, 46%). The zinc complex was synthesized by adding the solution of the Schiff base ligand (0.31 g, 1 mmol) in absolute ethanol (70 ml) to a solution of zinc nitrate hexahydrate (0.15 g, 0.5 mmol) in absolute ethanol (5 ml) and stirred under boiling condition for 10 min. A resultant yellow precipitate was separated and washed with hot ethanol (Yield: 0.29 g, 63%). Yellow single crystals of the title complex were crystallized from a mixture solution of chloroform/absolute ethanol (70:5 v/v) after 40 days at room temperature and further recrystallized from chloroform (40 ml) by slow evaporation at 296 K after 10 days, M.p 457–458 K.