Dichloridobis(thio­urea-κS)nickel(II)

Zouihri, H.

doi:10.1107/S1600536812006174

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m314

doi:10.1107/S1600536812006174

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Dichloridobis(thiourea-κS)nickel(II)

Hafid Zouihri ^a ^*

^aLaboratoire Privé de Cristallographie (LPC), Kénitra, Morocco
^*Correspondence e-mail: hafid.zouihri@gmail.com

(Received 11 February 2012; accepted 12 February 2012; online 24 February 2012)

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, C c
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[F² > 2σ(F²)] = 0.017
wR(F²) = 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)

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)
Symmetry codes: (i) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812006174/fj2518sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top

	Fig. 1. Molecular view of the title compound showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Projection of the title compound along the a axis showing two-dimensional networks lying parallel to the ab plane, H-bonds are represented by dashed lines.
	Fig. 3. Projection of the title compound along the b axis showing the three-dimensional arrangement of the title complexe, H-bonds are represented by dashed lines.

Dichloridobis(thiourea-κS)nickel(II) top

Crystal data top

[NiCl₂(CH₄N₂S)₂]	F(000) = 568
M_r = 281.85	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0205P)² + 0.1021P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
1695 reflections	Δρ_max = 0.25 e Å⁻³
132 parameters	Δρ_min = −0.15 e Å⁻³
10 restraints	Absolute structure: Flack (1983), 745 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.069 (10)

Crystal data top

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

Data collection top

Bruker APEXII CCD detector diffractometer	1695 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1678 reflections with I > 2σ(I)
T_min = 0.322, T_max = 0.622	R_int = 0.022
4883 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	All H-atom parameters refined
wR(F²) = 0.045	Δρ_max = 0.25 e Å⁻³
S = 1.08	Δρ_min = −0.15 e Å⁻³
1695 reflections	Absolute structure: Flack (1983), 745 Friedel pairs
132 parameters	Absolute structure parameter: 0.069 (10)
10 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x+1, y, z; (v) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[NiCl₂(CH₄N₂S)₂]
M_r	281.85
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	8.1578 (3), 11.8183 (5), 10.8526 (6)
β (°)	103.869 (2)
V (Å³)	1015.81 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.79
Crystal size (mm)	0.42 × 0.37 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.322, 0.622
No. of measured, independent and observed [I > 2σ(I)] reflections	4883, 1695, 1678
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.045, 1.08
No. of reflections	1695
No. of parameters	132
No. of restraints	10
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.15
Absolute structure	Flack (1983), 745 Friedel pairs
Absolute structure parameter	0.069 (10)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x+1, y, z; (v) x+1/2, −y+1/2, z+1/2.

Acknowledgements

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

References

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