Bis{S-benzyl 3-[(phen­yl)(pyridin-2-yl)methyl­idene]dithio­carbazato}zinc acetonitrile monosolvate

Thahira B S A Ravoof; Siti Aminah Omar; Mohamed Ibrahim Mohamed Tahir; Karen A Crouse

doi:10.1107/S1600536812009592

. 2012 Mar 10;68(Pt 4):m390–m391. doi: 10.1107/S1600536812009592

Bis{S-benzyl 3-[(phenyl)(pyridin-2-yl)methylidene]dithiocarbazato}zinc acetonitrile monosolvate

Thahira B S A Ravoof ^a,^*, Siti Aminah Omar ^a, Mohamed Ibrahim Mohamed Tahir ^a, Karen A Crouse ^a

PMCID: PMC3343804 PMID: 22589778

Abstract

In the title compound, [Zn(C₂₀H₁₆N₃S₂)₂]·CH₃CN, two different Schiff base moieties coordinate to the central Zn^II ion as tridentate N,N′,S-chelating ligands, creating a distorted octahedral environment [the smallest angle being 73.24 (6)° and the widest angle being 155.73 (7)°], with the two S atoms in cis positions. The dihedral angle between the mean planes of the two coordinating ligands is 83.65 (5)°. The crystal packing is consolidated by weak C—H⋯N hydrogen-bonding interactions.

Related literature

For background to the coordination chemistry of hydrazine carbodithioates, see: Ravoof et al. (2010 ▶). For the synthesis, see: Ravoof et al. (2004 ▶). For related structures, see: Hossain et al. (1996 ▶); Paulus et al. (2011 ▶). For H-atom treatment in the refinement, see: Cooper et al. (2010 ▶).

Experimental

Crystal data

[Zn(C₂₀H₁₆N₃S₂)₂]·C₂H₃N
M _r = 831.43
Monoclinic,
a = 12.5918 (3) Å
b = 14.0025 (3) Å
c = 22.2129 (5) Å
β = 100.429 (2)°
V = 3851.79 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 150 K
0.27 × 0.18 × 0.04 mm

Data collection

Oxford Diffraction Gemini CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.85, T _max = 0.96
17196 measured reflections
8678 independent reflections
7022 reflections with I > 2.0σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.081
S = 0.99
8677 reflections
487 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis PRO (Agilent, 2011 ▶); data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812009592/wm2598sup1.cif

e-68-0m390-sup1.cif^{(28.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009592/wm2598Isup2.hkl

e-68-0m390-Isup2.hkl^{(543.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn1—N102	2.1346 (17)
Zn1—S105	2.4403 (6)
Zn1—N115	2.2288 (17)
Zn1—N202	2.1160 (17)
Zn1—S205	2.4516 (6)
Zn1—N215	2.3188 (17)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C216—H2161⋯N103	0.95	2.62	3.285 (3)	127

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Acknowledgments

Support for this project came from Universiti Putra Malaysia (UPM) under the research University Grant Scheme (RUGS No. 05–01-11–1243RU) and the Malaysian Fundamental Research Grant Scheme (FRGS No: 01–03-11–986FR). SAO wishes to thank UPM for a Graduate Research Fellowship award.

supplementary crystallographic information

Comment

The title compound was preferentially formed during the synthesis of the tridentate Schiff base with zinc saccharinate, by eliminating the saccharinate anion and instead coordinating one metal ion with two tridentate deprotonated Schiff base moieties. Background on the coordination chemistry of hydrazine carbodithioates is given by Ravoof et al. (2010). Similar Cu(II) complexes have been previously synthesized by Hossain et al. (1996).

There is one independent molecule in the asymmetric unit which contains the Zn^II ion coordinated to two tridentate Schiff bases via the pyridyl nitrogen (N115, N215), azomethine nitrogen (N102, N202) and thiolate sulfur (S105, S205) atoms (Fig. 1). A solvent acetonitrile molecule in also present in the lattice. The coordination of the metal ion is distorted octahedral with equatorial angles ranging from 73.24 (6)° to 120.54 (5)°. The angle between the planes containing the atoms of the tridentate chelating rings is 83.65 (5). The planes containing the benzyl rings attached to the sulfur atom on both Schiff bases are almost parallel to each other with an angle of 16.41 (10). Similarly, the benzyl rings on the ketone moiety of the two Schiff bases are also almost parallel with an angle of 11.69 (9)°. However, the pyridine rings of the ketone moiety of the two Schiff bases are at an angle of 66.52 (10)°.

The packing diagram viewed along the b axis shows an arrangement where the benzyl ring of the ketone moiety of Schiff base 2 are arranged in such a way that it is facing each other between molecules. The crystal packing is consolidated by weak C—H···N hydrogen bonding interactions (Table 2).

For related structures, see: Hossain et al. (1996); Ravoof et al. (2010); Paulus et al. (2011).

Experimental

Zinc saccharinate, [Zn(sac)₂(H₂O)₄]. 2H₂O was prepared according to the method outlined in Ravoof et al. (2004). The 2-benzoylpyridine Schiff base of S-benzyldithiocarbazate was prepared following the method by Hossain et al. (1996). The Schiff base was dissolved in acetonitrile (50 ml) and mixed with an equimolar quantity of zinc saccharinate in acetonitrile (25 ml). The resulting mixture was heated on a water bath until the volume reduced to about 30 ml. On standing overnight, the mixture yielded orange crystals which were filtered off, washed with acetonitrile and dried in a desiccator over anhydrous silica gel, overnight. Crystals of the zinc complex suitable for X-ray diffraction analysis were obtained by recrystallisation from a mixture of acetonitrile, THF and chloroform. Slow evaporation over 3 weeks yielded crystals suitable for diffraction experiments.