Dichloridobis(thio-urea-κS)nickel(II).

The title complex, [NiCl(2)(CH(4)N(2)S)(2)], has been synthesized from the previously reported (diamino-methyl-idene)sulfonium chloride-thio-urea (3/2) salt [Zouihri (2012b ▶). Acta Cryst. E68, o257]. The Ni(II) ion is coordinated in a distorted tetra-hedral geometry by two mol-ecules of thio-urea [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 thio-urea ligands is 6.36 (15)°. The crystal structure is characterized by intra- and inter-molecular 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 NiII salts with thio­urea, see: Asif et al. (2010 ▶).

Experimental

Crystal data

[NiCl2(CH4N2S)2]

M = 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

Δρmax = 0.25 e Å−3

Δρmin = −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 ▶).

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

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

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

[NiCl2(CH4N2S)2]	F(000) = 568
Mr = 281.85	Dx = 1.843 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 289 reflections
a = 8.1578 (3) Å	θ = 1.8–26.7°
b = 11.8183 (5) Å	µ = 2.79 mm−1
c = 10.8526 (6) Å	T = 100 K
β = 103.869 (2)°	Prism, colourless
V = 1015.81 (8) Å3	0.42 × 0.37 × 0.17 mm
Z = 4

Bruker APEXII CCD detector diffractometer	1695 independent reflections
Radiation source: fine-focus sealed tube	1678 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω and φ scans	θmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→8
Tmin = 0.322, Tmax = 0.622	k = −14→14
4883 measured reflections	l = −13→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.017	All H-atom parameters refined
wR(F2) = 0.045	w = 1/[σ2(Fo2) + (0.0205P)2 + 0.1021P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.002
1695 reflections	Δρmax = 0.25 e Å−3
132 parameters	Δρmin = −0.15 e Å−3
10 restraints	Absolute structure: Flack (1983), 745 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.069 (10)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Ni1	0.15345 (3)	0.18215 (2)	0.53899 (3)	0.03234 (9)
Cl2	0.03840 (8)	0.33531 (5)	0.61305 (6)	0.03892 (15)
S2	0.33740 (7)	0.22386 (7)	0.41358 (6)	0.04019 (16)
S1	−0.05478 (8)	0.10041 (6)	0.38067 (5)	0.03680 (15)
Cl1	0.26641 (9)	0.06856 (6)	0.70409 (7)	0.04738 (16)
C1	−0.1912 (3)	0.03547 (18)	0.4566 (2)	0.0312 (5)
N1	−0.1424 (3)	0.0014 (2)	0.5748 (2)	0.0427 (5)
N2	−0.3484 (3)	0.0180 (2)	0.3936 (2)	0.0419 (5)
C2	0.5326 (3)	0.2585 (2)	0.5057 (2)	0.0341 (5)
N3	0.6387 (3)	0.3127 (2)	0.4532 (3)	0.0535 (7)
N4	0.5794 (3)	0.2294 (3)	0.6260 (2)	0.0562 (7)
H1A	−0.042 (3)	−0.001 (3)	0.618 (3)	0.054 (10)*
H2A	−0.412 (4)	−0.012 (3)	0.434 (3)	0.052 (9)*
H3A	0.597 (8)	0.333 (4)	0.376 (3)	0.13 (2)*
H4A	0.672 (3)	0.255 (3)	0.667 (3)	0.067 (11)*
H1B	−0.217 (4)	−0.033 (3)	0.599 (3)	0.048 (9)*
H2B	−0.392 (4)	0.048 (2)	0.327 (2)	0.039 (8)*
H3B	0.737 (4)	0.327 (4)	0.501 (5)	0.095 (17)*
H4B	0.513 (4)	0.186 (2)	0.656 (3)	0.046 (10)*

	U11	U22	U33	U12	U13	U23
Ni1	0.02675 (16)	0.03985 (16)	0.03008 (15)	−0.00044 (13)	0.00613 (11)	−0.00065 (13)
Cl2	0.0308 (3)	0.0446 (3)	0.0418 (3)	−0.0015 (2)	0.0094 (3)	−0.0120 (3)
S2	0.0226 (3)	0.0721 (4)	0.0250 (3)	−0.0055 (3)	0.0039 (2)	−0.0010 (3)
S1	0.0339 (3)	0.0500 (4)	0.0255 (3)	−0.0108 (3)	0.0052 (2)	−0.0026 (3)
Cl1	0.0441 (4)	0.0561 (4)	0.0385 (4)	0.0094 (3)	0.0032 (3)	0.0128 (3)
C1	0.0307 (12)	0.0278 (11)	0.0344 (13)	−0.0013 (9)	0.0063 (10)	−0.0036 (10)
N1	0.0366 (13)	0.0507 (13)	0.0385 (12)	−0.0128 (10)	0.0046 (10)	0.0096 (9)
N2	0.0301 (12)	0.0458 (14)	0.0462 (14)	−0.0054 (10)	0.0020 (10)	0.0098 (11)
C2	0.0230 (12)	0.0414 (13)	0.0366 (13)	0.0039 (10)	0.0045 (9)	−0.0070 (10)
N3	0.0270 (13)	0.0680 (18)	0.0648 (19)	−0.0072 (11)	0.0099 (13)	0.0030 (14)
N4	0.0326 (14)	0.095 (2)	0.0335 (13)	−0.0043 (14)	−0.0065 (11)	−0.0040 (14)

Ni1—Cl1	2.2516 (7)	N1—H1B	0.822 (18)
Ni1—Cl2	2.2726 (7)	N2—H2A	0.840 (19)
Ni1—S2	2.3079 (7)	N2—H2B	0.806 (18)
Ni1—S1	2.3177 (6)	C2—N3	1.312 (4)
S2—C2	1.715 (2)	C2—N4	1.315 (4)
S1—C1	1.716 (2)	N3—H3A	0.87 (2)
C1—N1	1.312 (3)	N3—H3B	0.86 (2)
C1—N2	1.317 (3)	N4—H4A	0.836 (19)
N1—H1A	0.843 (19)	N4—H4B	0.865 (19)
Cl1—Ni1—Cl2	108.56 (3)	H1A—N1—H1B	120 (3)
Cl1—Ni1—S2	113.37 (3)	C1—N2—H2A	116 (3)
Cl2—Ni1—S2	114.86 (3)	C1—N2—H2B	124 (2)
Cl1—Ni1—S1	115.40 (3)	H2A—N2—H2B	117 (4)
Cl2—Ni1—S1	107.62 (3)	N3—C2—N4	119.7 (3)
S2—Ni1—S1	96.69 (2)	N3—C2—S2	118.7 (2)
C2—S2—Ni1	110.56 (9)	N4—C2—S2	121.6 (2)
C1—S1—Ni1	105.95 (8)	C2—N3—H3A	114 (4)
N1—C1—N2	119.3 (2)	C2—N3—H3B	117 (4)
N1—C1—S1	121.80 (19)	H3A—N3—H3B	128 (6)
N2—C1—S1	118.9 (2)	C2—N4—H4A	116 (3)
C1—N1—H1A	126 (3)	C2—N4—H4B	118 (3)
C1—N1—H1B	113 (3)	H4A—N4—H4B	126 (4)

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···Cl2iv	0.86 (4)	2.47 (4)	3.317 (3)	168 (4)
N4—H4A···S2v	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)

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⋯Cl2iv	0.86 (4)	2.47 (4)	3.317 (3)	168 (4)
N4—H4A⋯S2v	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)

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