metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Crystal structure of di­chlorido­bis­­(1,3,4,5-tetra­methyl-1H-imidazol-2-ium-2-thiol­ate-κS)nickel(II)

aDepartment Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstrasse 100, D-33098 Paderborn, Germany
*Correspondence e-mail: ulrich.floerke@upb.de

Edited by E. F. C. Herdtweck, Technischen Universität München, Germany (Received 11 June 2015; accepted 26 June 2015; online 4 July 2015)

In the mol­ecular structure of the title compound, [NiCl2(C7H12N2S)2], the NiII atom has a distorted tetra­hedral geometry, coordinated by two Cl atoms [Ni—Cl= 2.2336 (6) Å] and two thione S atoms [Ni—S= 2.3024 (6) Å]. The angles at the NiII cation, which lies on a twofold rotation axis, are Cl—Ni—Cl = 115.58 (3)° and S—Ni—S = 94.55 (3)°. All other angles at the central NiII atom range from 109.46 (2) to 112.96 (2)°. The C—S—Ni angle is 99.91 (6)°. The planes of two imidazolium rings make a dihedral angle of 70.56 (6)°.

1. Related literature

For structures of related Ni complexes, see: Flörke et al. (2014[Flörke, U., Ahmida, A., Egold, H. & Henkel, G. (2014). Acta Cryst. E70, m384.]); O'Neill et al. (1981[O'Neill, M. E., Raper, E. S. & Daniels, J. A. (1981). Inorg. Chim. Acta, 54, L25-L27.]). For the ability of N,N-di­methyl­imidazole­thione derivatives to act as effective anti-oxidants, see: Bhabak & Mugesh (2010[Bhabak, K. P. & Mugesh, G. (2010). Chem. Eur. J. 16, 1175-1185.]); Yamashita & Yamashita (2010[Yamashita, Y. & Yamashita, M. (2010). J. Biol. Chem. pp. 285 jbc. C110.106377.]). For C—S bond lengths, see: Williams et al. (1997[Williams, D. J., Ly, T. A., Mudge, J. W., Pennington, W. T. & Schimek, G. L. (1997). Acta Cryst. C53, 415-416.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [NiCl2(C7H12N2S)2]

  • Mr = 442.10

  • Monoclinic, C 2/c

  • a = 14.8539 (17) Å

  • b = 8.5969 (10) Å

  • c = 16.4434 (19) Å

  • β = 112.104 (2)°

  • V = 1945.5 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.49 mm−1

  • T = 120 K

  • 0.43 × 0.20 × 0.14 mm

2.2. Data collection

  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004[Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.]) Tmin = 0.567, Tmax = 0.819

  • 8874 measured reflections

  • 2396 independent reflections

  • 2050 reflections with I > 2σ(I)

  • Rint = 0.033

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.089

  • S = 1.09

  • 2396 reflections

  • 109 parameters

  • H-atom parameters constrained

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2002[Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information


Structural commentary top

We are inter­ested in the chemistry of N,N-di­methyl­imidazole-thione derivatives due to their ability to act as effective anti­oxidants Bhabak et al. (2010); Yamashita et al. (2010). Complexes of the l-methyl derivative of imidazoline-2-thione with Zn(II) and NiII have been previously reported Flörke et al. (2014); O Neill et al., (1981). In our group we are inter­ested in this type of compound to be used in the synthesis of biomimetic complexes. Here we report the synthesis of NiII chloride complex with 1,3,4,5-tetra-methyl­imidazole-2-thione ligands. The title compound shows the same trans configuration as the di­chloro­biis(1,3-diiso­propyl-methyl-1H-2H.imidazole-2-thione-S)zinc(II) (Flörke et al., 2014). The Ni atom shows a distorted tetra­hedron with two chlorine atoms and two thione ligands, in which the angles at the Nickel cation are Cl—Ni—Cl 115.57 (3)° and S—Ni—S 94.55 (3)° . All other angles at the central Ni atom range from 109.46 (2)° to 112.96 (2)°. The Ni—S bond length is 2.2336 (6) Å. The C—S bond length in the title compound is elongated to 1.719 (2)Å by coordination to Nickel and closer to a single bond 1.81Å than a double bond 1.56Å (Williams et al., 1997). The intra­molecular hydrogen bonds between the chlorine atom and hydrogen atoms of methyl group, H2a—-Cl and H7b—-Cl amount to 3.093 and 3.557.respectively.

Synthesis and crystallization top

To a solution of 1,3,4,5-tetra-methyl­imidazoline-2-thione (0.390mg, 2.75mmol) in 40 ml aceto­nitrile, NiCl2 (0.162 mg, 1.25 mmol) ) was added and the mixture was stirred at room temperature for 24h. After removal of the solvent and subsequent drying in vacuum the residue was crystallized by diffusion of di­ethyl ether into a concentrated aceto­nitrile solution to give green single-crystals of the title complex.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H-atoms were clearly identified in difference syntheses and then refined at idealized positions riding on the carbon atoms with isotropic displacement parameters Uiso(H) = 1.5U(-CH3) and C–H 0.98 Å. All CH3 hydrogen atoms were allowed to rotate but not to tip.

Related literature top

For structures of related Ni complexes, see: Flörke et al. (2014); O'Neill et al. (1981). For the ability of N,N-dimethylimidazolethione derivatives to act as effective anti-oxidants, see: Bhabak & Mugesh (2010); Yamashita & Yamashita (2010). For C—S bond lengths, see: Williams et al. (1997).

Structure description top

We are inter­ested in the chemistry of N,N-di­methyl­imidazole-thione derivatives due to their ability to act as effective anti­oxidants Bhabak et al. (2010); Yamashita et al. (2010). Complexes of the l-methyl derivative of imidazoline-2-thione with Zn(II) and NiII have been previously reported Flörke et al. (2014); O Neill et al., (1981). In our group we are inter­ested in this type of compound to be used in the synthesis of biomimetic complexes. Here we report the synthesis of NiII chloride complex with 1,3,4,5-tetra-methyl­imidazole-2-thione ligands. The title compound shows the same trans configuration as the di­chloro­biis(1,3-diiso­propyl-methyl-1H-2H.imidazole-2-thione-S)zinc(II) (Flörke et al., 2014). The Ni atom shows a distorted tetra­hedron with two chlorine atoms and two thione ligands, in which the angles at the Nickel cation are Cl—Ni—Cl 115.57 (3)° and S—Ni—S 94.55 (3)° . All other angles at the central Ni atom range from 109.46 (2)° to 112.96 (2)°. The Ni—S bond length is 2.2336 (6) Å. The C—S bond length in the title compound is elongated to 1.719 (2)Å by coordination to Nickel and closer to a single bond 1.81Å than a double bond 1.56Å (Williams et al., 1997). The intra­molecular hydrogen bonds between the chlorine atom and hydrogen atoms of methyl group, H2a—-Cl and H7b—-Cl amount to 3.093 and 3.557.respectively.

For structures of related Ni complexes, see: Flörke et al. (2014); O'Neill et al. (1981). For the ability of N,N-dimethylimidazolethione derivatives to act as effective anti-oxidants, see: Bhabak & Mugesh (2010); Yamashita & Yamashita (2010). For C—S bond lengths, see: Williams et al. (1997).

Synthesis and crystallization top

To a solution of 1,3,4,5-tetra-methyl­imidazoline-2-thione (0.390mg, 2.75mmol) in 40 ml aceto­nitrile, NiCl2 (0.162 mg, 1.25 mmol) ) was added and the mixture was stirred at room temperature for 24h. After removal of the solvent and subsequent drying in vacuum the residue was crystallized by diffusion of di­ethyl ether into a concentrated aceto­nitrile solution to give green single-crystals of the title complex.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H-atoms were clearly identified in difference syntheses and then refined at idealized positions riding on the carbon atoms with isotropic displacement parameters Uiso(H) = 1.5U(-CH3) and C–H 0.98 Å. All CH3 hydrogen atoms were allowed to rotate but not to tip.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with anisotropic displacement parameters drawn at the 50% probability level.
Dichloridobis(1,3,4,5-tetramethyl-1H-imidazol-2-ium-2-thiolate-κS)nickel(II) top
Crystal data top
[NiCl2(C7H12N2S)2]F(000) = 920
Mr = 442.10Dx = 1.509 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 14.8539 (17) ÅCell parameters from 2710 reflections
b = 8.5969 (10) Åθ = 2.7–28.3°
c = 16.4434 (19) ŵ = 1.49 mm1
β = 112.104 (2)°T = 120 K
V = 1945.5 (4) Å3Prism, green
Z = 40.43 × 0.20 × 0.14 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2396 independent reflections
Radiation source: sealed tube2050 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
φ and ω scansθmax = 28.2°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 1919
Tmin = 0.567, Tmax = 0.819k = 1110
8874 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: difference Fourier map
wR(F2) = 0.089H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0492P)2 + 0.3156P]
where P = (Fo2 + 2Fc2)/3
2396 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
[NiCl2(C7H12N2S)2]V = 1945.5 (4) Å3
Mr = 442.10Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.8539 (17) ŵ = 1.49 mm1
b = 8.5969 (10) ÅT = 120 K
c = 16.4434 (19) Å0.43 × 0.20 × 0.14 mm
β = 112.104 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2396 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
2050 reflections with I > 2σ(I)
Tmin = 0.567, Tmax = 0.819Rint = 0.033
8874 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.09Δρmax = 0.56 e Å3
2396 reflectionsΔρmin = 0.27 e Å3
109 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
xyzUiso*/Ueq
Ni10.00000.47837 (4)0.25000.02273 (12)
Cl10.05106 (4)0.61687 (7)0.16067 (3)0.03670 (15)
S10.11606 (3)0.29666 (6)0.32329 (3)0.02693 (14)
N10.22435 (11)0.46213 (18)0.46966 (10)0.0225 (3)
N20.27871 (11)0.48030 (18)0.36568 (10)0.0235 (3)
C10.20753 (13)0.4178 (2)0.38685 (12)0.0222 (4)
C20.16219 (14)0.4241 (3)0.51751 (13)0.0292 (4)
H2A0.11440.50720.50920.044*
H2B0.20200.41350.58010.044*
H2C0.12830.32590.49540.044*
C30.30709 (13)0.5538 (2)0.50124 (12)0.0237 (4)
C40.34399 (15)0.6198 (2)0.59158 (12)0.0305 (4)
H4A0.39940.68810.59930.046*
H4B0.36460.53510.63450.046*
H4C0.29230.67980.60040.046*
C50.34120 (13)0.5658 (2)0.43585 (12)0.0250 (4)
C60.42680 (14)0.6509 (3)0.43159 (14)0.0338 (5)
H6A0.46240.70060.48830.051*
H6B0.40460.73060.38570.051*
H6C0.46970.57760.41800.051*
C70.28996 (15)0.4587 (3)0.28167 (13)0.0306 (5)
H7A0.34210.38370.28900.046*
H7B0.30630.55850.26190.046*
H7C0.22900.41960.23800.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02009 (19)0.0228 (2)0.02449 (19)0.0000.00747 (14)0.000
Cl10.0332 (3)0.0404 (3)0.0408 (3)0.0038 (2)0.0189 (2)0.0134 (2)
S10.0247 (2)0.0242 (3)0.0280 (3)0.00122 (18)0.00545 (19)0.00048 (18)
N10.0203 (7)0.0249 (9)0.0229 (8)0.0024 (6)0.0087 (6)0.0042 (6)
N20.0219 (8)0.0263 (9)0.0227 (8)0.0042 (6)0.0086 (6)0.0054 (6)
C10.0209 (8)0.0233 (10)0.0228 (9)0.0049 (7)0.0085 (7)0.0055 (7)
C20.0271 (10)0.0386 (12)0.0262 (10)0.0002 (8)0.0150 (8)0.0044 (8)
C30.0219 (9)0.0223 (10)0.0260 (9)0.0022 (7)0.0078 (7)0.0047 (7)
C40.0337 (11)0.0298 (11)0.0270 (10)0.0017 (8)0.0101 (8)0.0010 (8)
C50.0219 (9)0.0253 (10)0.0260 (9)0.0015 (7)0.0071 (7)0.0057 (8)
C60.0275 (10)0.0394 (12)0.0354 (11)0.0042 (9)0.0130 (8)0.0091 (9)
C70.0314 (11)0.0398 (12)0.0247 (10)0.0059 (9)0.0153 (8)0.0041 (9)
Geometric parameters (Å, º) top
Ni1—Cl12.2336 (6)C2—H2C0.9800
Ni1—Cl1i2.2337 (6)C3—C51.354 (3)
Ni1—S1i2.3024 (6)C3—C41.489 (3)
Ni1—S12.3024 (6)C4—H4A0.9800
S1—C11.719 (2)C4—H4B0.9800
N1—C11.344 (2)C4—H4C0.9800
N1—C31.386 (2)C5—C61.492 (3)
N1—C21.458 (2)C6—H6A0.9800
N2—C11.343 (2)C6—H6B0.9800
N2—C51.388 (2)C6—H6C0.9800
N2—C71.464 (2)C7—H7A0.9800
C2—H2A0.9800C7—H7B0.9800
C2—H2B0.9800C7—H7C0.9800
Cl1—Ni1—Cl1i115.58 (3)C5—C3—C4131.00 (18)
Cl1—Ni1—S1i112.96 (2)N1—C3—C4122.16 (17)
Cl1i—Ni1—S1i109.46 (2)C3—C4—H4A109.5
Cl1—Ni1—S1109.46 (2)C3—C4—H4B109.5
Cl1i—Ni1—S1112.96 (2)H4A—C4—H4B109.5
S1i—Ni1—S194.55 (3)C3—C4—H4C109.5
C1—S1—Ni199.91 (6)H4A—C4—H4C109.5
C1—N1—C3109.97 (16)H4B—C4—H4C109.5
C1—N1—C2124.69 (16)C3—C5—N2106.67 (17)
C3—N1—C2125.30 (17)C3—C5—C6130.91 (18)
C1—N2—C5109.99 (16)N2—C5—C6122.42 (18)
C1—N2—C7125.03 (17)C5—C6—H6A109.5
C5—N2—C7124.97 (17)C5—C6—H6B109.5
N2—C1—N1106.54 (16)H6A—C6—H6B109.5
N2—C1—S1127.15 (14)C5—C6—H6C109.5
N1—C1—S1126.23 (15)H6A—C6—H6C109.5
N1—C2—H2A109.5H6B—C6—H6C109.5
N1—C2—H2B109.5N2—C7—H7A109.5
H2A—C2—H2B109.5N2—C7—H7B109.5
N1—C2—H2C109.5H7A—C7—H7B109.5
H2A—C2—H2C109.5N2—C7—H7C109.5
H2B—C2—H2C109.5H7A—C7—H7C109.5
C5—C3—N1106.84 (16)H7B—C7—H7C109.5
Cl1i—Ni1—S1—C163.57 (7)C1—N1—C3—C50.2 (2)
Cl1—Ni1—S1—C166.74 (7)C2—N1—C3—C5177.55 (18)
S1i—Ni1—S1—C1176.95 (7)C1—N1—C3—C4179.83 (17)
C5—N2—C1—N10.2 (2)C2—N1—C3—C42.4 (3)
C7—N2—C1—N1178.56 (17)N1—C3—C5—N20.3 (2)
C5—N2—C1—S1177.22 (14)C4—C3—C5—N2179.72 (19)
C7—N2—C1—S11.6 (3)N1—C3—C5—C6179.12 (19)
C3—N1—C1—N20.0 (2)C4—C3—C5—C60.9 (4)
C2—N1—C1—N2177.77 (17)C1—N2—C5—C30.3 (2)
C3—N1—C1—S1177.06 (14)C7—N2—C5—C3178.45 (18)
C2—N1—C1—S15.2 (3)C1—N2—C5—C6179.15 (17)
Ni1—S1—C1—N289.72 (16)C7—N2—C5—C62.1 (3)
Ni1—S1—C1—N193.84 (16)
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formula[NiCl2(C7H12N2S)2]
Mr442.10
Crystal system, space groupMonoclinic, C2/c
Temperature (K)120
a, b, c (Å)14.8539 (17), 8.5969 (10), 16.4434 (19)
β (°) 112.104 (2)
V3)1945.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.49
Crystal size (mm)0.43 × 0.20 × 0.14
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.567, 0.819
No. of measured, independent and
observed [I > 2σ(I)] reflections
8874, 2396, 2050
Rint0.033
(sin θ/λ)max1)0.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.089, 1.09
No. of reflections2396
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.27

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008) and local programs.

 

References

First citationBhabak, K. P. & Mugesh, G. (2010). Chem. Eur. J. 16, 1175–1185.  Web of Science CrossRef CAS PubMed Google Scholar
First citationBruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFlörke, U., Ahmida, A., Egold, H. & Henkel, G. (2014). Acta Cryst. E70, m384.  CSD CrossRef IUCr Journals Google Scholar
First citationO'Neill, M. E., Raper, E. S. & Daniels, J. A. (1981). Inorg. Chim. Acta, 54, L25–L27.  CAS Google Scholar
First citationSheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWilliams, D. J., Ly, T. A., Mudge, J. W., Pennington, W. T. & Schimek, G. L. (1997). Acta Cryst. C53, 415–416.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationYamashita, Y. & Yamashita, M. (2010). J. Biol. Chem. pp. 285 jbc. C110.106377.  Google Scholar

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