Chlorido[1-(4,5-dihydro-1,3-thia­zol-2-yl-κN)ethanone thio­semicarbazonato-κ² N ¹,S]nickel(II)

Abstract

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,

• a = 9.656 (2) Å

• b = 10.617 (2) Å

• c = 11.187 (3) Å

• β = 112.874 (4)°

• V = 1056.7 (4) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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 ▶).

Supplementary Material

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
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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All hydrogen atoms attached to carbon and nitrogen atoms were positioned geometrically and refined as riding, with C—H = 0.96–0.97Å, N—H = 0.86Å and U_iso(H) = 1.2(1.5 for methyl group) U_eq(C,N).

Figures

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.

Crystal data

[Ni(C6H9N4S2)Cl]	F(000) = 600
Mr = 295.45	Dx = 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

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

Refinement

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(Fo2) + (0.0327P)2] where P = (Fo2 + 2Fc2)/3
2554 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.