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

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

doi:10.1107/S1600536808002262

. 2008 Jan 25;64(Pt 2):m416–m417. doi: 10.1107/S1600536808002262

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

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

PMCID: PMC2960465 PMID: 21201362

Abstract

The Cu^II atom of the title complex, [Cu(C₁₇H₁₅N₂S₂)₂], lies on a twofold rotation axis, and is in a distorted tetrahedral geometry with the two bidentate N₂S₂ Schiff bases. In the crystal structure, the molecules are interconnected into chains along the c axis by weak C—H⋯S intermolecular interactions. The crystal packing is further stabilized by C—H⋯π interactions.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For the synthesis and structures of S-benzyldithiocarbazates, see: Ali & Tarafder (1977 ▶); Shanmuga Sundara Raj et al. (2000 ▶). For related Cu^II complexes, see: Ali et al. (2008 ▶); Castiñeiras et al. (1998 ▶); Goswami & Eichhorn (2000 ▶). For bioactivities of S-benzyldithiocarbazate metal complexes, see: Ali et al. (2002 ▶, 2008 ▶); Tarafder et al. (2001 ▶, 2002 ▶).

Experimental

Crystal data

[Cu(C₁₇H₁₅N₂S₂)₂]
M _r = 686.45
Orthorhombic,
a = 36.1410 (7) Å
b = 9.9372 (2) Å
c = 8.7598 (2) Å
V = 3146.00 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 100.0 (1) K
0.57 × 0.29 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.603, T _max = 0.906
84850 measured reflections
6922 independent reflections
5675 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.083
S = 1.04
6922 reflections
196 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.43 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/S1600536808002262/ci2558sup1.cif

e-64-0m416-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808002262/ci2558Isup2.hkl

e-64-0m416-Isup2.hkl^{(338.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—N1	2.0663 (10)
Cu1—S1	2.2649 (3)

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N1ⁱ—Cu1—N1	104.29 (5)
N1—Cu1—S1ⁱ	86.94 (3)
N1—Cu1—S1	121.90 (3)
S1ⁱ—Cu1—S1	134.452 (19)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯S2ⁱⁱ	0.93	2.76	3.6698 (15)	167
C11—H11A⋯Cg1ⁱⁱⁱ	0.97	2.98	3.5806 (14)	121

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

Acknowledgments

MTHT and MTI thank Rajshahi University for financial support. The authors 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

Synthesis (Ali & Tarafder, 1977) and crystal structure (Shanmuga Sundara Raj et al., 2000) of S-benzyldithiocarbazate (SBDTC) have been reported. We have been greatly involved in the chemistry of Schiff bases derived from SBDTC, and also on their metal complexes because of their interesting physico-chemical properties and potentially useful biological activities (Ali et al., 2002, 2008; Tarafder et al., 2001, 2002). In continuation of our interests, we report herein the syntheses of the cinnamaldehyde Schiff base of SBDTC and its copper complex, along with the x-ray structural analysis of the four-coordinated Cu^II complex.

The Cu^II atom of the title complex, lies on a twofold rotation axis and the asymmetric unit therefore contains one-half of a molecule (Fig. 1). Based on other thiosemicarbazones (Ali et al., 2002; Tarafder et al., 2001, 2002), the coordination mode of the Cu^II complex is as expected, i.e bis-chelated through the two azomethine nitrogen atoms and the two thiolate sulfur atoms. The Cu^II center is in a distorted tetrahedral geometry with the N₂S₂ donor atoms of the two Schiff base ligands (Fig. 1). Both nitrogen atoms (N1 and N1A) and sulfur atoms (S1 and S1A) from the two ligands are coordinated at opposite positions. The N—Cu—N and S—Cu—S bond angles are 104.29 (5)° and 134.452 (14)°, respectively, and reflective of the elongation of the Cu—S bond length [ca 0.19 Å] over the Cu—N bond length. The Cu1—N1 and Cu1—S1 distances of 2.0663 (10) Å and 2.2648 (3) Å, respectively, are in the same range as those in other four coordination Cu^II complexes of the related Schiff base ligands (Ali et al., 2008; Castiñeiras et al., 1998; Goswami & Eichhorn, 2000). The Cu^II-bidentate rings are slightly non-planar. The Cu1—S1—N1A—N2A—C10 ring has a maximum deviation of 0.085 (1) Å for the N1A atom. The mean plane of the propenyl moiety (C7/C8/C9) makes a dihedral angle of 12.15 (9)° with mean plane of the attached C1–C6 benzene ring. The dihedral angle between the C1–C6 and C12–C17 phenyl rings of the two ligands is 8.73 (7)°. Bond lengths and angles observed in the Schiff base ligand are of normal values (Allen et al., 1987).

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 structure is further stabilized by C—H···π interactions (Table 2) involving the C1—C6 benzene ring (centroid Cg1).

Experimental

The Schiff base ligand was prepared 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), as reported previously (Ali & Tarafder, 1977). The mixture was refluxed for 10 min. The yellow precipitate which formed was isolated and washed with hot ethanol. The yellow solid product was recrystallized from absolute ethanol (yield: 1.52 g, 46%). The copper complex was synthesized by adding the copper nitrate trihydrate (0.31 g, 0.5 mmol) in ethanol (10 ml) to a hot solution of the above Schiff base ligand (0.31 g, 1 mmol) in ethanol (80 ml) and the reaction mixture was refluxed for 5 min when a brownish precipitate was formed. The product was separated and washed with hot ethanol (yield: 0.32 g, 74%). Green single crystals of the title complex were recrystallized from a chloroform-absolute ethanol (10:3 V/V) solution after 20 d at room temperature.