Chlorido[1-(4,5-dihydro-1,3-thia­zol-2-yl-κN)ethanone thio­semicarbazonato-κ2N1,S]nickel(II)

Viñuelas-Zahínos, E.; Luna-Giles, F.; Torres-García, P.; Bernalte-García, Á.

doi:10.1107/S1600536810051500

metal-organic compounds

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Volume 67| Part 1| January 2011| Page m79

https://doi.org/10.1107/S1600536810051500

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Chlorido[1-(4,5-dihydro-1,3-thiazol-2-yl-κN)ethanone thiosemicarbazonato-κ²N¹,S]nickel(II)

Emilio Viñuelas-Zahínos,^a Francisco Luna-Giles,^a Pablo Torres-García ^a and Álvaro Bernalte-García ^a ^*

^aDepartamento de Quimica Organica e Inorganica, Facultad de Ciencias, Universidad de Extremadura, Badajoz, Spain
^*Correspondence e-mail: emilvin@unex.es

(Received 22 November 2010; accepted 8 December 2010; online 15 December 2010)

In the title compound, [Ni(C₆H₉N₄S₂)Cl], the Ni atom is in a slightly distorted square-planar environment coordinated by a Cl atom and a deprotonated thiosemicarbazone ligand via its thiazoline N, azomethine N and thiolate S atoms. Short intermolecular N—H⋯Cl and C—H⋯S contacts are present in the crystal structure.

Related literature

For the structure of the organic ligand and several metal complexes, see: Viñuelas-Zahínos et al. (2011). For the structures of closely related nickel complexes, see: Liu et al. (1999 ); Philip et al. (2004 ); Swearingen et al. (2002 ).

Experimental

Crystal data

[Ni(C₆H₉N₄S₂)Cl]
M_r = 295.45
Monoclinic, P 2₁ /c
a = 9.656 (2) Å
b = 10.617 (2) Å
c = 11.187 (3) Å
β = 112.874 (4)°
V = 1056.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.45 mm⁻¹
T = 298 K
0.22 × 0.15 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.615, T_max = 0.828
2554 measured reflections
2554 independent reflections
1758 reflections with 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.076
S = 1.05
2554 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯Clⁱ	0.86	2.51	3.310 (3)	155
N4—H4A⋯Clⁱⁱ	0.86	2.53	3.373 (3)	166
C3—H3B⋯S1ⁱⁱⁱ	0.97	2.98	3.537 (3)	118
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810051500/rk2251sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051500/rk2251Isup2.hkl

checkCIF report

Comment top

The preceding study reports the metal complexes of 1–(4,5–dihydro–1,3–thiazol–2–yl)ethanone thiosemicarbazone (HATtsc) (Viñuelas–Zahínos et al., 2011). It should be pointed out that in nickel complex the organic ligand is deprotonated and shifts from the thione to the thiolate form, in such a way that the negative charge is delocalized between the two bonds S2—C6 and N3—C6, as it is observed in other nickel complexes with thiosemicarbazone ligands (Liu et al., 1999; Philip et al., 2004; Swearingen et al., 2002). Another difference in complex with respect to the structure of the free ligand HATtsc is the degree of rotation around the C1—C4 and C6—N3 bonds, which permits coordination through N1 and S2. In crystal structure there are the following short intermolecular contacts: N4—H4A···Cl, N4—H4B···Cl and C3—H3B···S1.

Related literature top

For the structure of the organic ligand and several metal complexes, see: Viñuelas-Zahínos et al. (2011). For the structures of closely related nickel complexes, see: Liu et al. (1999); Philip et al. (2004); Swearingen et al. (2002).

Experimental top

1-(4,5-dihydro-1,3-thiazol-2-yl)ethanone thiosemicarbazone (HATtsc) was synthesized as according to a literature procedure (Viñuelas-Zahínos et al., 2010). A solution containing NiCl₂^.6H₂O (58.5 mg, 0.25 mmol) in 1 ml ethanol:acetonitrile (2:1) was added to a solution (40 ml) of HATtsc (50.0 mg, 0.25 mmol) in ethanol:acetonitrile (2:1). The brown product was recrystallized from ethanol:methanol (1:1) to give brown crystals.

Structure description top

For the structure of the organic ligand and several metal complexes, see: Viñuelas-Zahínos et al. (2011). For the structures of closely related nickel complexes, see: Liu et al. (1999); Philip et al. (2004); Swearingen et al. (2002).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. A view of molecular structure of title compound, showing the atom–numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

Chlorido[1-(4,5-dihydro-1,3-thiazol-2-yl-κN)ethanone thiosemicarbazonato-κ²N¹,S]nickel(II) top

Crystal data top

[Ni(C₆H₉N₄S₂)Cl]	F(000) = 600
M_r = 295.45	D_x = 1.857 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 912 reflections
a = 9.656 (2) Å	θ = 2.3–26.3°
b = 10.617 (2) Å	µ = 2.45 mm⁻¹
c = 11.187 (3) Å	T = 298 K
β = 112.874 (4)°	Prism, brown
V = 1056.7 (4) Å³	0.22 × 0.15 × 0.08 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	2554 independent reflections
Radiation source: fine–focus sealed tube	1758 reflections with 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −12→11
T_min = 0.615, T_max = 0.828	k = 0→14
2554 measured reflections	l = 0→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0327P)²] where P = (F_o² + 2F_c²)/3
2554 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Ni(C₆H₉N₄S₂)Cl]	V = 1056.7 (4) Å³
M_r = 295.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.656 (2) Å	µ = 2.45 mm⁻¹
b = 10.617 (2) Å	T = 298 K
c = 11.187 (3) Å	0.22 × 0.15 × 0.08 mm
β = 112.874 (4)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2554 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1758 reflections with 2σ(I)
T_min = 0.615, T_max = 0.828	R_int = 0.030
2554 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.05	Δρ_max = 0.33 e Å⁻³
2554 reflections	Δρ_min = −0.34 e Å⁻³
128 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
C1	0.3581 (3)	0.6235 (2)	0.0701 (2)	0.0334 (6)
C2	0.3833 (3)	0.4480 (2)	0.1999 (3)	0.0426 (7)
H2A	0.4210	0.4551	0.2936	0.051*
H2B	0.4086	0.3650	0.1783	0.051*
C3	0.2123 (3)	0.4657 (3)	0.1417 (3)	0.0504 (8)
H3A	0.1753	0.4759	0.2103	0.06*
H3B	0.1639	0.3926	0.0905	0.06*
C4	0.4210 (3)	0.7245 (2)	0.0176 (2)	0.0340 (6)
C5	0.3317 (3)	0.8206 (3)	−0.0777 (3)	0.0460 (7)
H5A	0.3662	0.9032	−0.0445	0.069*
H5B	0.2275	0.8121	−0.0919	0.069*
H5C	0.3438	0.8085	−0.1581	0.069*
C6	0.7922 (3)	0.7897 (2)	0.0918 (3)	0.0385 (6)
Cl	0.75176 (8)	0.43164 (6)	0.31254 (7)	0.0474 (2)
N1	0.4522 (2)	0.5445 (2)	0.1476 (2)	0.0361 (5)
N2	0.5671 (2)	0.71858 (19)	0.0663 (2)	0.0333 (5)
N3	0.6450 (2)	0.8074 (2)	0.0291 (2)	0.0399 (6)
N4	0.8837 (3)	0.8692 (2)	0.0669 (2)	0.0552 (7)
H4A	0.8472	0.9292	0.0121	0.066*
H4B	0.9795	0.8606	0.1057	0.066*
Ni	0.65556 (4)	0.58829 (3)	0.18229 (3)	0.03380 (12)
S1	0.17043 (8)	0.60537 (7)	0.03983 (8)	0.0493 (2)
S2	0.86881 (8)	0.66908 (7)	0.20402 (7)	0.0465 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0295 (14)	0.0359 (14)	0.0342 (15)	−0.0026 (11)	0.0119 (12)	−0.0042 (12)
C2	0.0445 (17)	0.0365 (15)	0.0506 (19)	−0.0033 (13)	0.0225 (15)	0.0017 (13)
C3	0.0422 (17)	0.0473 (17)	0.061 (2)	−0.0105 (14)	0.0187 (16)	0.0021 (15)
C4	0.0331 (15)	0.0317 (14)	0.0340 (15)	0.0010 (11)	0.0094 (12)	−0.0004 (11)
C5	0.0394 (16)	0.0458 (17)	0.0475 (18)	0.0044 (13)	0.0112 (14)	0.0105 (14)
C6	0.0358 (15)	0.0396 (15)	0.0441 (17)	−0.0061 (12)	0.0199 (13)	−0.0028 (13)
Cl	0.0398 (4)	0.0440 (4)	0.0541 (5)	0.0087 (3)	0.0137 (3)	0.0101 (3)
N1	0.0314 (12)	0.0359 (12)	0.0403 (13)	−0.0027 (10)	0.0131 (10)	0.0025 (10)
N2	0.0303 (12)	0.0333 (12)	0.0369 (13)	−0.0006 (9)	0.0137 (10)	0.0004 (10)
N3	0.0393 (13)	0.0383 (13)	0.0458 (14)	−0.0047 (10)	0.0206 (12)	0.0030 (11)
N4	0.0351 (14)	0.0576 (16)	0.0727 (19)	−0.0084 (12)	0.0207 (13)	0.0112 (14)
Ni	0.02818 (19)	0.03349 (19)	0.0382 (2)	0.00139 (15)	0.01121 (15)	0.00176 (15)
S1	0.0281 (4)	0.0485 (5)	0.0661 (5)	−0.0031 (3)	0.0126 (4)	0.0033 (4)
S2	0.0293 (4)	0.0486 (4)	0.0578 (5)	−0.0008 (3)	0.0128 (3)	0.0060 (4)

Geometric parameters (Å, º) top

C1—N1	1.292 (3)	C5—H5B	0.96
C1—C4	1.463 (3)	C5—H5C	0.96
C1—S1	1.720 (3)	C6—N4	1.327 (3)
C2—N1	1.462 (3)	C6—N3	1.332 (3)
C2—C3	1.533 (4)	C6—S2	1.743 (3)
C2—H2A	0.97	Cl—Ni	2.1679 (8)
C2—H2B	0.97	N1—Ni	1.905 (2)
C3—S1	1.817 (3)	N2—N3	1.367 (3)
C3—H3A	0.97	N2—Ni	1.861 (2)
C3—H3B	0.97	N4—H4A	0.86
C4—N2	1.302 (3)	N4—H4B	0.86
C4—C5	1.485 (3)	Ni—S2	2.1554 (9)
C5—H5A	0.96

N1—C1—C4	116.9 (2)	H5B—C5—H5C	109.5
N1—C1—S1	118.2 (2)	N4—C6—N3	117.4 (3)
C4—C1—S1	124.9 (2)	N4—C6—S2	119.2 (2)
N1—C2—C3	109.1 (2)	N3—C6—S2	123.4 (2)
N1—C2—H2A	109.9	C1—N1—C2	114.4 (2)
C3—C2—H2A	109.9	C1—N1—Ni	112.27 (18)
N1—C2—H2B	109.9	C2—N1—Ni	133.07 (18)
C3—C2—H2B	109.9	C4—N2—N3	118.3 (2)
H2A—C2—H2B	108.3	C4—N2—Ni	117.17 (18)
C2—C3—S1	107.85 (19)	N3—N2—Ni	124.56 (16)
C2—C3—H3A	110.1	C6—N3—N2	110.0 (2)
S1—C3—H3A	110.1	C6—N4—H4A	120
C2—C3—H3B	110.1	C6—N4—H4B	120
S1—C3—H3B	110.1	H4A—N4—H4B	120
H3A—C3—H3B	108.4	N2—Ni—N1	83.24 (9)
N2—C4—C1	110.4 (2)	N2—Ni—S2	86.68 (7)
N2—C4—C5	124.5 (2)	N1—Ni—S2	169.68 (7)
C1—C4—C5	125.2 (2)	N2—Ni—Cl	177.76 (7)
C4—C5—H5A	109.5	N1—Ni—Cl	95.06 (7)
C4—C5—H5B	109.5	S2—Ni—Cl	95.08 (3)
H5A—C5—H5B	109.5	C1—S1—C3	90.43 (13)
C4—C5—H5C	109.5	C6—S2—Ni	95.27 (9)
H5A—C5—H5C	109.5

N1—C2—C3—S1	−3.3 (3)	C4—N2—Ni—N1	0.65 (19)
N1—C1—C4—N2	−3.2 (3)	N3—N2—Ni—N1	−179.2 (2)
S1—C1—C4—N2	174.88 (19)	C4—N2—Ni—S2	−177.17 (19)
N1—C1—C4—C5	176.9 (2)	N3—N2—Ni—S2	3.02 (19)
S1—C1—C4—C5	−5.1 (4)	C1—N1—Ni—N2	−2.43 (19)
C4—C1—N1—C2	178.3 (2)	C2—N1—Ni—N2	−175.7 (3)
S1—C1—N1—C2	0.1 (3)	C1—N1—Ni—S2	9.8 (5)
C4—C1—N1—Ni	3.7 (3)	C2—N1—Ni—S2	−163.5 (3)
S1—C1—N1—Ni	−174.50 (12)	C1—N1—Ni—Cl	179.02 (18)
C3—C2—N1—C1	2.2 (3)	C2—N1—Ni—Cl	5.7 (2)
C3—C2—N1—Ni	175.34 (19)	N1—C1—S1—C3	−1.9 (2)
C1—C4—N2—N3	−179.1 (2)	C4—C1—S1—C3	−179.9 (2)
C5—C4—N2—N3	0.8 (4)	C2—C3—S1—C1	2.9 (2)
C1—C4—N2—Ni	1.1 (3)	N4—C6—S2—Ni	−178.7 (2)
C5—C4—N2—Ni	−179.0 (2)	N3—C6—S2—Ni	1.6 (2)
N4—C6—N3—N2	−179.5 (2)	N2—Ni—S2—C6	−2.03 (11)
S2—C6—N3—N2	0.1 (3)	N1—Ni—S2—C6	−14.2 (4)
C4—N2—N3—C6	177.7 (2)	Cl—Ni—S2—C6	176.58 (9)
Ni—N2—N3—C6	−2.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···Clⁱ	0.86	2.51	3.310 (3)	155
N4—H4A···Clⁱⁱ	0.86	2.53	3.373 (3)	166
C3—H3B···S1ⁱⁱⁱ	0.97	2.98	3.537 (3)	118

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₉N₄S₂)Cl]
M_r	295.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.656 (2), 10.617 (2), 11.187 (3)
β (°)	112.874 (4)
V (Å³)	1056.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.45
Crystal size (mm)	0.22 × 0.15 × 0.08

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.615, 0.828
No. of measured, independent and observed [2σ(I)] reflections	2554, 2554, 1758
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.076, 1.05
No. of reflections	2554
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.34

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···Clⁱ	0.86	2.51	3.310 (3)	155.4
N4—H4A···Clⁱⁱ	0.86	2.53	3.373 (3)	165.8
C3—H3B···S1ⁱⁱⁱ	0.97	2.98	3.537 (3)	117.6

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z.

Acknowledgements

The authors would like to thank the Junta de Extremadura (III PRI+D+I) and the FEDER (project PRI08A022) for support.

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