Crystal structure of bis­[S-hexyl 3-(4-methyl­benzyl­idene)di­thio­carbazato-κ2 N 3,S]nickel(II)

M B H Howlader; M S Begum; M C Sheikh; R Miyatake; E Zangrando

doi:10.1107/S2056989015000328

. 2015 Jan 14;71(Pt 2):m26–m27. doi: 10.1107/S2056989015000328

Crystal structure of bis[S-hexyl 3-(4-methylbenzylidene)dithiocarbazato-κ² N ³,S]nickel(II)

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

PMCID: PMC4384570 PMID: 25878838

Abstract

In the title complex, [Ni(C₁₅H₂₁N₂S₂)₂], the Ni^II atom exhibits a square-planar coordination geometry and is located on an inversion centre leading to a trans configuration of the N,S-chelating ligands. In the crystal, the complex molecules stack at a distance of 4.6738 (3) Å along the a axis, which exclude any significant interactions between the aromatic rings.

Keywords: crystal structure, nickel complex, dithiocarbazate

Related literature

For the structures of related complexes, see: Chan et al. (2008 ▸); Islam et al. (2011 ▸, 2014 ▸); Li et al. (2006 ▸); Zhang et al. (2004 ▸). For the structure of the ligand, see: Howlader et al. (2015 ▸).

Experimental

Crystal data

[Ni(C₁₅H₂₁N₂S₂)₂]
M _r = 645.62
Triclinic,
a = 4.6738 (3) Å
b = 10.5132 (5) Å
c = 16.4789 (8) Å
α = 86.522 (3)°
β = 84.850 (3)°
γ = 79.057 (3)°
V = 791.00 (7) Å³
Z = 1
Cu Kα radiation
μ = 3.55 mm⁻¹
T = 173 K
0.37 × 0.08 × 0.02 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ▸) T _min = 0.615, T _max = 0.932
9100 measured reflections
2834 independent reflections
2029 reflections with F ² > 2σ(F ²)
R _int = 0.074

Refinement

R[F ² > 2σ(F ²)] = 0.071
wR(F ²) = 0.218
S = 1.09
2834 reflections
180 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.35 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/S2056989015000328/ds2244sup1.cif

e-71-00m26-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000328/ds2244Isup2.hkl

e-71-00m26-Isup2.hkl^{(155.7KB, hkl)}

Click here for additional data file.^{(32.1KB, tif)}

ORTEP L 2 . DOI: 10.1107/S2056989015000328/ds2244fig1.tif

ORTEP drawing (ellipsoid probability at 50%) of the centrosymmetric NiL ₂ complex.

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015000328/ds2244fig2.tif

Crystal packing of the complex.

CCDC reference: 1035820

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

Table 1. Selected bond lengths ().

NiN1	1.933 (3)
NiS1	2.1775 (10)

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Acknowledgments

MBHH 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. Structural commentary

The metal is located on a crystallographic inversion centre and the two Schiff bases, in their deprotonated imino thiolate form, act as chelating ligands to the metal centre via the azomethine nitrogen N1 and thiolate sulphur S1 atoms in a trans-planar configuration as imposed by the crystal symmetry. The complex has coplanar geometry with the exception of the hexyl chains that pend hedgewise. In the complex, the Ni—S and Ni–N bond distances are of 2.1777 (11) and 1.933 (4) Å, respectively, with a S(2)—Ni—N(2) chelating angle of 86.06 (10)°. These geometrical parameters agree with those reported for similar nickel complexes either when ligands assume a trans (Islam, et al., 2011; Islam, et al., 2014; Zhang, et al., 2004) or a cis configuration (Chan, et al., 2008; Li, et al., 2006). The ligand, recently reported (Howlader, et al., 2015), underwent rotation about the C9—N2 by 180° in order to allow the N,S chelating behavior towards the metal. Upon coordination some salient features are observed with respect to the free ligand, and the most significant are an elongation of the C(9)—S(1) bond length (1.720 (4) Å in NiL₂ that must be compared to 1.670 (3) Å in HL, thus validating the coordination with deprotonated thiolate sulphur atom. Correspondingly the N(2)—C(9) bond length, of 1.335 (3) Å, shortens to 1.270 (6) Å in the NiL₂ complex, while the N(1)—N(2) bond length of 1.375 (3) Å in HL is slightly elongated in the complex (1.426 (5) Å, Table 1).

S2. Supramolecular features

The complexes stack at a distance of 4.6738 (3) Å (axis a), which exclude any significant interactions between the aromatic rings.

S3. Synthesis and crystallization

A solution of Ni(CH₃COO)₂.4H₂O (0.06 g, 0.25 mmol, 8 mL methanol) was added to a solution of the ligand, S-hexyl (E)-3-(4-methylbenzylidene)dithiocarbazate, (0.15 g, 0.5 mmol, 10 mL methanol ). The resulting mixture was stirred at room temperature for four hours. A dark reddish brown precipitate was formed, filtered off, washed with methanol and dried in vacuo over anhydrous CaCl₂. Dark reddish brown single crystals, suitable for X-ray diffraction, of the compound were obtained by slow evaporation from a mixture of chloroform and acetonitrile (1:1) after 7 days. M.P. 374 K.

S4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located geometrically and treated as riding atoms, with C—H = 0.95–0.99 Å, and with Uĩso~(H) = 1.2U~eq~(C) or 1.5U~eq~(C) for methyl H atoms.