metal-organic compounds
H-imidazol-2-ium-2-thiolate-κS)nickel(II)
of dichloridobis(1,3,4,5-tetramethyl-1aDepartment Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstrasse 100, D-33098 Paderborn, Germany
*Correspondence e-mail: ulrich.floerke@upb.de
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)°.
CCDC reference: 1408996
1. Related literature
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).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Supporting information
CCDC reference: 1408996
https://doi.org/10.1107/S2056989015012281/hp2071sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012281/hp2071Isup2.hkl
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.
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.
Crystal data, data collection and structure
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.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).
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.
detailsCrystal data, data collection and structure
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.Data collection: SMART (Bruker, 2002); cell
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.Fig. 1. Molecular structure of the title compound with anisotropic displacement parameters drawn at the 50% probability level. |
[NiCl2(C7H12N2S)2] | F(000) = 920 |
Mr = 442.10 | Dx = 1.509 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.8539 (17) Å | Cell parameters from 2710 reflections |
b = 8.5969 (10) Å | θ = 2.7–28.3° |
c = 16.4434 (19) Å | µ = 1.49 mm−1 |
β = 112.104 (2)° | T = 120 K |
V = 1945.5 (4) Å3 | Prism, green |
Z = 4 | 0.43 × 0.20 × 0.14 mm |
Bruker SMART CCD area-detector diffractometer | 2396 independent reflections |
Radiation source: sealed tube | 2050 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 28.2°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −19→19 |
Tmin = 0.567, Tmax = 0.819 | k = −11→10 |
8874 measured reflections | l = −21→21 |
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)] = 0.035 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.089 | H-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 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
[NiCl2(C7H12N2S)2] | V = 1945.5 (4) Å3 |
Mr = 442.10 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.8539 (17) Å | µ = 1.49 mm−1 |
b = 8.5969 (10) Å | T = 120 K |
c = 16.4434 (19) Å | 0.43 × 0.20 × 0.14 mm |
β = 112.104 (2)° |
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 = 0.819 | Rint = 0.033 |
8874 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.56 e Å−3 |
2396 reflections | Δρmin = −0.27 e Å−3 |
109 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.47837 (4) | 0.2500 | 0.02273 (12) | |
Cl1 | 0.05106 (4) | 0.61687 (7) | 0.16067 (3) | 0.03670 (15) | |
S1 | 0.11606 (3) | 0.29666 (6) | 0.32329 (3) | 0.02693 (14) | |
N1 | 0.22435 (11) | 0.46213 (18) | 0.46966 (10) | 0.0225 (3) | |
N2 | 0.27871 (11) | 0.48030 (18) | 0.36568 (10) | 0.0235 (3) | |
C1 | 0.20753 (13) | 0.4178 (2) | 0.38685 (12) | 0.0222 (4) | |
C2 | 0.16219 (14) | 0.4241 (3) | 0.51751 (13) | 0.0292 (4) | |
H2A | 0.1144 | 0.5072 | 0.5092 | 0.044* | |
H2B | 0.2020 | 0.4135 | 0.5801 | 0.044* | |
H2C | 0.1283 | 0.3259 | 0.4954 | 0.044* | |
C3 | 0.30709 (13) | 0.5538 (2) | 0.50124 (12) | 0.0237 (4) | |
C4 | 0.34399 (15) | 0.6198 (2) | 0.59158 (12) | 0.0305 (4) | |
H4A | 0.3994 | 0.6881 | 0.5993 | 0.046* | |
H4B | 0.3646 | 0.5351 | 0.6345 | 0.046* | |
H4C | 0.2923 | 0.6798 | 0.6004 | 0.046* | |
C5 | 0.34120 (13) | 0.5658 (2) | 0.43585 (12) | 0.0250 (4) | |
C6 | 0.42680 (14) | 0.6509 (3) | 0.43159 (14) | 0.0338 (5) | |
H6A | 0.4624 | 0.7006 | 0.4883 | 0.051* | |
H6B | 0.4046 | 0.7306 | 0.3857 | 0.051* | |
H6C | 0.4697 | 0.5776 | 0.4180 | 0.051* | |
C7 | 0.28996 (15) | 0.4587 (3) | 0.28167 (13) | 0.0306 (5) | |
H7A | 0.3421 | 0.3837 | 0.2890 | 0.046* | |
H7B | 0.3063 | 0.5585 | 0.2619 | 0.046* | |
H7C | 0.2290 | 0.4196 | 0.2380 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02009 (19) | 0.0228 (2) | 0.02449 (19) | 0.000 | 0.00747 (14) | 0.000 |
Cl1 | 0.0332 (3) | 0.0404 (3) | 0.0408 (3) | 0.0038 (2) | 0.0189 (2) | 0.0134 (2) |
S1 | 0.0247 (2) | 0.0242 (3) | 0.0280 (3) | 0.00122 (18) | 0.00545 (19) | 0.00048 (18) |
N1 | 0.0203 (7) | 0.0249 (9) | 0.0229 (8) | 0.0024 (6) | 0.0087 (6) | 0.0042 (6) |
N2 | 0.0219 (8) | 0.0263 (9) | 0.0227 (8) | 0.0042 (6) | 0.0086 (6) | 0.0054 (6) |
C1 | 0.0209 (8) | 0.0233 (10) | 0.0228 (9) | 0.0049 (7) | 0.0085 (7) | 0.0055 (7) |
C2 | 0.0271 (10) | 0.0386 (12) | 0.0262 (10) | 0.0002 (8) | 0.0150 (8) | 0.0044 (8) |
C3 | 0.0219 (9) | 0.0223 (10) | 0.0260 (9) | 0.0022 (7) | 0.0078 (7) | 0.0047 (7) |
C4 | 0.0337 (11) | 0.0298 (11) | 0.0270 (10) | −0.0017 (8) | 0.0101 (8) | 0.0010 (8) |
C5 | 0.0219 (9) | 0.0253 (10) | 0.0260 (9) | 0.0015 (7) | 0.0071 (7) | 0.0057 (8) |
C6 | 0.0275 (10) | 0.0394 (12) | 0.0354 (11) | −0.0042 (9) | 0.0130 (8) | 0.0091 (9) |
C7 | 0.0314 (11) | 0.0398 (12) | 0.0247 (10) | 0.0059 (9) | 0.0153 (8) | 0.0041 (9) |
Ni1—Cl1 | 2.2336 (6) | C2—H2C | 0.9800 |
Ni1—Cl1i | 2.2337 (6) | C3—C5 | 1.354 (3) |
Ni1—S1i | 2.3024 (6) | C3—C4 | 1.489 (3) |
Ni1—S1 | 2.3024 (6) | C4—H4A | 0.9800 |
S1—C1 | 1.719 (2) | C4—H4B | 0.9800 |
N1—C1 | 1.344 (2) | C4—H4C | 0.9800 |
N1—C3 | 1.386 (2) | C5—C6 | 1.492 (3) |
N1—C2 | 1.458 (2) | C6—H6A | 0.9800 |
N2—C1 | 1.343 (2) | C6—H6B | 0.9800 |
N2—C5 | 1.388 (2) | C6—H6C | 0.9800 |
N2—C7 | 1.464 (2) | C7—H7A | 0.9800 |
C2—H2A | 0.9800 | C7—H7B | 0.9800 |
C2—H2B | 0.9800 | C7—H7C | 0.9800 |
Cl1—Ni1—Cl1i | 115.58 (3) | C5—C3—C4 | 131.00 (18) |
Cl1—Ni1—S1i | 112.96 (2) | N1—C3—C4 | 122.16 (17) |
Cl1i—Ni1—S1i | 109.46 (2) | C3—C4—H4A | 109.5 |
Cl1—Ni1—S1 | 109.46 (2) | C3—C4—H4B | 109.5 |
Cl1i—Ni1—S1 | 112.96 (2) | H4A—C4—H4B | 109.5 |
S1i—Ni1—S1 | 94.55 (3) | C3—C4—H4C | 109.5 |
C1—S1—Ni1 | 99.91 (6) | H4A—C4—H4C | 109.5 |
C1—N1—C3 | 109.97 (16) | H4B—C4—H4C | 109.5 |
C1—N1—C2 | 124.69 (16) | C3—C5—N2 | 106.67 (17) |
C3—N1—C2 | 125.30 (17) | C3—C5—C6 | 130.91 (18) |
C1—N2—C5 | 109.99 (16) | N2—C5—C6 | 122.42 (18) |
C1—N2—C7 | 125.03 (17) | C5—C6—H6A | 109.5 |
C5—N2—C7 | 124.97 (17) | C5—C6—H6B | 109.5 |
N2—C1—N1 | 106.54 (16) | H6A—C6—H6B | 109.5 |
N2—C1—S1 | 127.15 (14) | C5—C6—H6C | 109.5 |
N1—C1—S1 | 126.23 (15) | H6A—C6—H6C | 109.5 |
N1—C2—H2A | 109.5 | H6B—C6—H6C | 109.5 |
N1—C2—H2B | 109.5 | N2—C7—H7A | 109.5 |
H2A—C2—H2B | 109.5 | N2—C7—H7B | 109.5 |
N1—C2—H2C | 109.5 | H7A—C7—H7B | 109.5 |
H2A—C2—H2C | 109.5 | N2—C7—H7C | 109.5 |
H2B—C2—H2C | 109.5 | H7A—C7—H7C | 109.5 |
C5—C3—N1 | 106.84 (16) | H7B—C7—H7C | 109.5 |
Cl1i—Ni1—S1—C1 | −63.57 (7) | C1—N1—C3—C5 | 0.2 (2) |
Cl1—Ni1—S1—C1 | 66.74 (7) | C2—N1—C3—C5 | −177.55 (18) |
S1i—Ni1—S1—C1 | −176.95 (7) | C1—N1—C3—C4 | −179.83 (17) |
C5—N2—C1—N1 | −0.2 (2) | C2—N1—C3—C4 | 2.4 (3) |
C7—N2—C1—N1 | 178.56 (17) | N1—C3—C5—N2 | −0.3 (2) |
C5—N2—C1—S1 | −177.22 (14) | C4—C3—C5—N2 | 179.72 (19) |
C7—N2—C1—S1 | 1.6 (3) | N1—C3—C5—C6 | 179.12 (19) |
C3—N1—C1—N2 | 0.0 (2) | C4—C3—C5—C6 | −0.9 (4) |
C2—N1—C1—N2 | 177.77 (17) | C1—N2—C5—C3 | 0.3 (2) |
C3—N1—C1—S1 | 177.06 (14) | C7—N2—C5—C3 | −178.45 (18) |
C2—N1—C1—S1 | −5.2 (3) | C1—N2—C5—C6 | −179.15 (17) |
Ni1—S1—C1—N2 | −89.72 (16) | C7—N2—C5—C6 | 2.1 (3) |
Ni1—S1—C1—N1 | 93.84 (16) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [NiCl2(C7H12N2S)2] |
Mr | 442.10 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 14.8539 (17), 8.5969 (10), 16.4434 (19) |
β (°) | 112.104 (2) |
V (Å3) | 1945.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.49 |
Crystal size (mm) | 0.43 × 0.20 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.567, 0.819 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8874, 2396, 2050 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.089, 1.09 |
No. of reflections | 2396 |
No. of parameters | 109 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.27 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008) and local programs.
References
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