trans-Bis(4,6-dimethyl­pyrimidine-2-thiol­ato-κ2N,S)bis­(thio­urea-κS)nickel(II)

Zhu, J.; Wang, J.-G.; Duan, T.; Zhang, Q.-F.

doi:10.1107/S1600536809050223

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1697

doi:10.1107/S1600536809050223

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trans-Bis(4,6-dimethylpyrimidine-2-thiolato-κ²N,S)bis(thiourea-κS)nickel(II)

Jing Zhu,^a Jian-Gang Wang,^a Taike Duan ^a ^* and Qian-Feng Zhang ^a

^aInstitute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma'anshan, Anhui 243002, People's Republic of China
^*Correspondence e-mail: imc@ahut.edu.cn

(Received 10 November 2009; accepted 22 November 2009; online 28 November 2009)

In the title complex, [Ni(C₆H₇N₂S)₂(CH₄N₂S)₂], the central Ni atom (located on a centre of inversion) is six-coordinated by two monoanionic N,S-chelating 4,6-dimethylpyrimidine-2-thiolate ligands and two trans S-coordinating thiourea groups. The trans-N₂S₄ donor set defines a distorted octahedral geometry.

Related literature

For the significance of transition-metal complexes of heterocyclic thione ligands, see: Dilworth & Hu (1993 ); Figgis & Reynolds (1986 ); Zamudio-Rivera et al. (2005 ). For related structures, see: Rodríguez et al. (2007 ); Weininger et al. (1969 ).

Experimental

Crystal data

[Ni(C₆H₇N₂S)₂(CH₄N₂S)₂]
M_r = 489.35
Orthorhombic, P b c a
a = 15.0306 (2) Å
b = 8.5783 (1) Å
c = 16.9274 (2) Å
V = 2182.57 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 296 K
0.12 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.861, T_max = 0.901
17226 measured reflections
2495 independent reflections
1542 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.101
S = 1.07
2495 reflections
126 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050223/tk2572sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050223/tk2572Isup2.hkl

checkCIF report

Comment top

There has been extensive interest in transition metal complexes of heterocyclic thione ligands, and their thiolate derivatives, due to the potential relevance of such compounds as models of active sites in metalloenzymes and their ability to adopt structures of variable nuclearity (Dilworth & Hu, 1993). Pyrimidine-2-thione (pymtH), a typical heterocyclic thione ligand, is a versatile sulfur donor ligand in terms of coordination modes (Zamudio-Rivera et al., 2005). In this paper, we report the synthesis and crystal structure of a mononuclear nickel(II) complex of 4,6-dimethylpyrimidine-2-thione (dmpymtH), namely trans-Ni(NH₂CSNH₂)₂(dmpymt)₂, (I).

In (I), Fig. 1, the nickel atom is located on a centre of inversion. The monoanionic dmpymt ligand functions as a chelating ligand through the S atom and one of the N atoms to form a four-membered NiSCN chelate ring. The Ni—S(dmpymt) and Ni—N bond lengths are 2.4798 (7) and 2.060 (2) Å, respectively. The N—Ni—S(dmpymt) chelate angle of 68.83 (6) ° is similar to those found in the other hexacoordinate metal complexes containing anionic heterocyclic thiolate N,S-chelate ligands (Rodríguez et al., 2007). The heterocyclic thiolate ligand is essentially planar with a maximum deviation of 0.009 (2) Å from the least-squares plane for atom N1. The thiourea ligand is terminally bound to the Ni atom via coordination of the S2 atom. The Ni—S(thiourea) bond length (2.4888 (8) Å) is similar to those in trans-NiCl₂(NH₂CSNH₂)₄ (2.470 (1) Å) (Figgis & Reynolds, 1986) and [Ni(NH₂CSNH₂)₆]Br₂ (2.506 (1) Å) (Weininger et al., 1969).

Related literature top

For the significance of transition-metal complexes of heterocyclic thione ligands, see: Dilworth & Hu (1993); Figgis & Reynolds (1986); Zamudio-Rivera et al. (2005). For related structures, see: Rodríguez et al. (2007); Weininger et al. (1969).

Experimental top

Treatment of a mixture of dmpymt (28 mg, 0.20 mmol) and thiourea (16 mg, 0.20 mmol) in methanol (10 ml) with Ni(NO₃)₂.6H₂O (30 mg, 0.10 mmol) in methanol (10 ml) gave a light-green solution. The homogeneous solution was stirred for 2 h at 60 °, and then filtered. Slow evaporation of the solvent gave a green solid, which was recrystallized from CH₂Cl₂/Et₂O to give dark-green blocks of (I) Yield: 48 mg, ca. 46% (based on Ni). Anal. Calcd. for C₁₄H₂₂N₈NiS₄: C, 34.4; H, 4.53; N, 22.9%. Found: C, 34.2; H, 4.50; N, 22.3%.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level. The Ni atom lies ona centre of inversion and unlabelled atoms are related by the symmetry operation 2-x, -y, 1-z.

trans-Bis(4,6-dimethylpyrimidine-2-thiolato- κ²N,S)bis(thiourea-κS)nickel(II) top

Crystal data top

[Ni(C₆H₇N₂S)₂(CH₄N₂S)₂]	F(000) = 1016
M_r = 489.35	D_x = 1.489 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2124 reflections
a = 15.0306 (2) Å	θ = 2.4–20.9°
b = 8.5783 (1) Å	µ = 1.29 mm⁻¹
c = 16.9274 (2) Å	T = 296 K
V = 2182.57 (5) Å³	Bar, green
Z = 4	0.12 × 0.12 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2495 independent reflections
Radiation source: fine-focus sealed tube	1542 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
phi and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −12→19
T_min = 0.861, T_max = 0.901	k = −11→11
17226 measured reflections	l = −21→21

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0412P)²] where P = (F_o² + 2F_c²)/3
2495 reflections	(Δ/σ)_max = 0.001
126 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Ni(C₆H₇N₂S)₂(CH₄N₂S)₂]	V = 2182.57 (5) Å³
M_r = 489.35	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 15.0306 (2) Å	µ = 1.29 mm⁻¹
b = 8.5783 (1) Å	T = 296 K
c = 16.9274 (2) Å	0.12 × 0.12 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2495 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	1542 reflections with I > 2σ(I)
T_min = 0.861, T_max = 0.901	R_int = 0.061
17226 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.07	Δρ_max = 0.27 e Å⁻³
2495 reflections	Δρ_min = −0.30 e Å⁻³
126 parameters

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	1.0000	0.0000	0.5000	0.03228 (16)
S1	1.01100 (5)	0.11627 (9)	0.36624 (4)	0.0379 (2)
S2	0.99725 (5)	0.28135 (9)	0.53580 (5)	0.0452 (2)
N1	0.87628 (14)	0.0228 (2)	0.44894 (13)	0.0335 (5)
N2	0.83917 (16)	0.1316 (3)	0.32332 (13)	0.0456 (6)
N3	0.92492 (18)	0.2365 (3)	0.67697 (14)	0.0571 (8)
H3A	0.9032	0.2694	0.7209	0.068*
H3B	0.9267	0.1382	0.6672	0.068*
N4	0.9512 (2)	0.4872 (3)	0.64286 (17)	0.0654 (8)
H4A	0.9291	0.5162	0.6873	0.078*
H4B	0.9707	0.5556	0.6100	0.078*
C1	0.89783 (18)	0.0895 (3)	0.37873 (16)	0.0336 (6)
C2	0.7691 (2)	−0.0829 (5)	0.54075 (19)	0.0657 (10)
H2A	0.8090	−0.1687	0.5491	0.099*
H2B	0.7090	−0.1207	0.5394	0.099*
H2C	0.7754	−0.0091	0.5830	0.099*
C3	0.7906 (2)	−0.0057 (3)	0.46408 (18)	0.0428 (8)
C4	0.7263 (2)	0.0366 (4)	0.40970 (19)	0.0575 (10)
H4	0.6664	0.0186	0.4200	0.069*
C5	0.7525 (2)	0.1057 (4)	0.34018 (18)	0.0554 (9)
C6	0.6865 (2)	0.1604 (5)	0.2792 (2)	0.0953 (15)
H6A	0.7143	0.2356	0.2453	0.143*
H6B	0.6364	0.2074	0.3052	0.143*
H6C	0.6667	0.0731	0.2484	0.143*
C7	0.9555 (2)	0.3363 (4)	0.62490 (17)	0.0416 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0289 (3)	0.0400 (3)	0.0280 (3)	0.0001 (2)	0.0017 (2)	0.0070 (2)
S1	0.0374 (4)	0.0437 (4)	0.0327 (4)	−0.0003 (4)	0.0069 (3)	0.0059 (3)
S2	0.0548 (5)	0.0385 (4)	0.0423 (5)	−0.0011 (4)	0.0081 (4)	0.0016 (3)
N1	0.0282 (12)	0.0417 (14)	0.0304 (13)	−0.0005 (11)	0.0009 (10)	0.0044 (11)
N2	0.0409 (15)	0.0643 (18)	0.0317 (13)	0.0069 (13)	−0.0066 (12)	0.0038 (12)
N3	0.085 (2)	0.0480 (16)	0.0380 (15)	−0.0051 (16)	0.0154 (15)	−0.0092 (13)
N4	0.087 (2)	0.0444 (18)	0.0643 (19)	0.0023 (16)	0.0046 (18)	−0.0123 (14)
C1	0.0341 (16)	0.0353 (16)	0.0314 (15)	0.0052 (13)	−0.0019 (13)	−0.0016 (13)
C2	0.044 (2)	0.097 (3)	0.056 (2)	−0.014 (2)	0.0104 (18)	0.019 (2)
C3	0.0318 (17)	0.059 (2)	0.0375 (17)	−0.0024 (15)	0.0056 (14)	0.0005 (15)
C4	0.0306 (18)	0.092 (3)	0.050 (2)	0.0030 (18)	−0.0033 (16)	−0.0025 (19)
C5	0.040 (2)	0.084 (3)	0.0422 (18)	0.0046 (19)	−0.0097 (15)	−0.0002 (18)
C6	0.055 (2)	0.167 (4)	0.064 (2)	0.012 (3)	−0.025 (2)	0.024 (3)
C7	0.0420 (18)	0.0407 (17)	0.0421 (17)	0.0009 (15)	−0.0100 (15)	−0.0058 (16)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	2.060 (2)	N4—C7	1.330 (3)
Ni1—N1	2.060 (2)	N4—H4A	0.8600
Ni1—S1	2.4798 (7)	N4—H4B	0.8600
Ni1—S1ⁱ	2.4798 (7)	C2—C3	1.493 (4)
Ni1—S2	2.4888 (8)	C2—H2A	0.9600
Ni1—S2ⁱ	2.4888 (8)	C2—H2B	0.9600
S1—C1	1.729 (3)	C2—H2C	0.9600
S2—C7	1.700 (3)	C3—C4	1.383 (4)
N1—C3	1.336 (3)	C4—C5	1.375 (4)
N1—C1	1.358 (3)	C4—H4	0.9300
N2—C1	1.337 (3)	C5—C6	1.506 (4)
N2—C5	1.352 (4)	C6—H6A	0.9600
N3—C7	1.312 (4)	C6—H6B	0.9600
N3—H3A	0.8600	C6—H6C	0.9600
N3—H3B	0.8600

N1ⁱ—Ni1—N1	180.0	N2—C1—N1	124.8 (2)
N1ⁱ—Ni1—S1	111.17 (6)	N2—C1—S1	121.8 (2)
N1—Ni1—S1	68.83 (6)	N1—C1—S1	113.42 (19)
N1ⁱ—Ni1—S1ⁱ	68.83 (6)	C3—C2—H2A	109.5
N1—Ni1—S1ⁱ	111.17 (6)	C3—C2—H2B	109.5
S1—Ni1—S1ⁱ	180.0	H2A—C2—H2B	109.5
N1ⁱ—Ni1—S2	90.28 (6)	C3—C2—H2C	109.5
N1—Ni1—S2	89.72 (6)	H2A—C2—H2C	109.5
S1—Ni1—S2	80.41 (3)	H2B—C2—H2C	109.5
S1ⁱ—Ni1—S2	99.59 (3)	N1—C3—C4	119.8 (3)
N1ⁱ—Ni1—S2ⁱ	89.72 (6)	N1—C3—C2	117.2 (3)
N1—Ni1—S2ⁱ	90.28 (6)	C4—C3—C2	123.0 (3)
S1—Ni1—S2ⁱ	99.59 (3)	C5—C4—C3	118.9 (3)
S1ⁱ—Ni1—S2ⁱ	80.41 (3)	C5—C4—H4	120.6
S2—Ni1—S2ⁱ	180.0	C3—C4—H4	120.6
C1—S1—Ni1	76.66 (9)	N2—C5—C4	121.8 (3)
C7—S2—Ni1	119.41 (11)	N2—C5—C6	116.0 (3)
C3—N1—C1	118.3 (2)	C4—C5—C6	122.1 (3)
C3—N1—Ni1	140.6 (2)	C5—C6—H6A	109.5
C1—N1—Ni1	101.06 (16)	C5—C6—H6B	109.5
C1—N2—C5	116.3 (3)	H6A—C6—H6B	109.5
C7—N3—H3A	120.0	C5—C6—H6C	109.5
C7—N3—H3B	120.0	H6A—C6—H6C	109.5
H3A—N3—H3B	120.0	H6B—C6—H6C	109.5
C7—N4—H4A	120.0	N3—C7—N4	117.7 (3)
C7—N4—H4B	120.0	N3—C7—S2	123.0 (2)
H4A—N4—H4B	120.0	N4—C7—S2	119.3 (2)

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₇N₂S)₂(CH₄N₂S)₂]
M_r	489.35
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	15.0306 (2), 8.5783 (1), 16.9274 (2)
V (Å³)	2182.57 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.12 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.861, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	17226, 2495, 1542
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.101, 1.07
No. of reflections	2495
No. of parameters	126
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.30

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This project was supported by the Program for New Century Excellent Talents in Universities of China (NCET-06–0556 and NCET-08–0618).

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