Dichloridobis(thio­urea-κS)nickel(II)

Hafid Zouihri

doi:10.1107/S1600536812006174

. 2012 Feb 24;68(Pt 3):m314. doi: 10.1107/S1600536812006174

Dichloridobis(thiourea-κS)nickel(II)

Hafid Zouihri ^a,^*

PMCID: PMC3297264 PMID: 22412454

Abstract

The title complex, [NiCl₂(CH₄N₂S)₂], has been synthesized from the previously reported (diaminomethylidene)sulfonium chloride–thiourea (3/2) salt [Zouihri (2012b ▶). Acta Cryst. E68, o257]. The Ni^II ion is coordinated in a distorted tetrahedral geometry by two molecules of thiourea [Ni—S = 2.3079 (7) and 2.3177 (6) Å] and two chloride anions [Ni—Cl = 2.2516 (7) and 2.2726 (7) Å]. The bond angles at the Ni atom lie between 96.69 (2) and 115.40 (3)°, while the dihedral angle between the mean planes of the two thiourea ligands is 6.36 (15)°. The crystal structure is characterized by intra- and intermolecular N—H⋯Cl hydrogen bonds, which lead to the formation of two-dimensional networks lying parallel to the ab plane. The networks are linked via classical N—H⋯Cl and N—H⋯S hydrogen bonds, forming a three-dimensional arrangement.

Related literature

For the synthesis and the crystal structure of (diaminomethylidene)sulfonium chloride thiourea (3/2), see: Zouihri (2012b ▶). For related structures, see: Ambujam et al. (2007 ▶); Zouihri (2012a ▶). For related literature on the coordination complexes of Ni^II salts with thiourea, see: Asif et al. (2010 ▶).

Experimental

Crystal data

[NiCl₂(CH₄N₂S)₂]
M _r = 281.85
Monoclinic,
a = 8.1578 (3) Å
b = 11.8183 (5) Å
c = 10.8526 (6) Å
β = 103.869 (2)°
V = 1015.81 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.79 mm⁻¹
T = 100 K
0.42 × 0.37 × 0.17 mm

Data collection

Bruker APEXII CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.322, T _max = 0.622
4883 measured reflections
1695 independent reflections
1678 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.017
wR(F ²) = 0.045
S = 1.08
1695 reflections
132 parameters
10 restraints
All H-atom parameters refined
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ▶), 745 Friedel pairs
Flack parameter: 0.069 (10)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812006174/fj2518sup1.cif

e-68-0m314-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006174/fj2518Isup2.hkl

e-68-0m314-Isup2.hkl^{(83.5KB, 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
N1—H1A⋯Cl1	0.84 (3)	2.60 (3)	3.388 (3)	157 (3)
N1—H1B⋯Cl2ⁱ	0.83 (3)	2.56 (3)	3.365 (3)	164 (3)
N2—H2A⋯Cl2ⁱ	0.83 (3)	2.75 (3)	3.499 (2)	150 (3)
N2—H2B⋯Cl2ⁱⁱ	0.81 (2)	2.64 (2)	3.432 (2)	166 (3)
N3—H3A⋯Cl1ⁱⁱⁱ	0.86 (3)	2.83 (5)	3.423 (3)	128 (5)
N3—H3B⋯Cl2^iv	0.86 (4)	2.47 (4)	3.317 (3)	168 (4)
N4—H4A⋯S2^v	0.84 (3)	2.70 (3)	3.366 (2)	137 (3)
N4—H4B⋯Cl1	0.86 (3)	2.60 (3)	3.448 (3)	168 (3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The author thanks the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

supplementary crystallographic information

Comment

Nickel^(II), which has a d⁸ configuration, commonly exhibits octahedral, square planar and tetrahedral coordination geometries depending upon the nature of the ligands and the Crystal Field Splitting Parameter value.

In our case, the coordination complexes of Ni^(II) salts with thiourea show a variety of compositions and types of coordination (octahedral, tetragonal, square-planar and tetrahedral) (Asif et al. 2010). In general, the predominant coordination geometries for the Ni^(II)-Ligand-X (X= Cl^-, Br^- and I^-) are Tetragonal (Ni^(II)L₄)X₂ and Octahedral (Ni^(II)L₆)X₂. Tetrakis coordiantion of thiourea about Nickel Ni(Th)₄Cl₂ has been found in centered tetragonal symmetry class I4 by K. Ambujam (Ambujam et al. 2007).

In former work we have reported the synthesis and crystal structure of the catena-poly[[chlorido(thiourea-κS)copper(I)]-µ-thiourea-κ²S:S] complexe (Zouihri, 2012a). In this paper we report the crystal structure of [Ni^(II)(Th)₂] 2Cl^- which has been synthetized from the (Diaminomethylidene)sulfonium chloride-thiourea (3/2) (Zouihri, 2012b).

In the title complexe compound, (SCN₂H₄)₂Ni^(II)Cl₂, The Ni^(II) atom is four coordinated in a tetrahedral geometry by two molecules of thiourea (average Ni—S distance = 2.3079 (7) to 2.3177 (6) Å) and two chloride anions (average Ni—Cl distance = 2.2516 (7) to 2.2726 (7) Å) with average (S, Cl)—Ni^II—(S, Cl) torsion angles between 96.69 (2)° and 115.40 (3)°. The dihedral angle between the two thiourea Ligands is: 6.36 (15)°.

The crystal structure is characterized by intramolecular and intermolecular N—H···Cl hydrogen bonds which lead to the formation of two-dimensional networks lying parallel to the ab plane (Fig. 2 and Table 1). The networks are linked via classical intermolecular N—H···Cl and N—H···S hydrogen bonds, forming a three-dimensional arrangement (Fig. 3 and Table 1).

Experimental

To a 10 ml aqueous solution of NiCl2 (2 mmol) was added 10 ml EtOH solution of (Diaminomethylidene)sulfonium chloride-thiourea (3/2) (Zouihri, 2012b) (1.0 mmol). Colourless crystal were obtained after about one week.