Dichloridobis(1,3-diisopropyl-4,5-di­methyl-1H-imidazol-3-ium-2-thiol­ate-κS)copper(II)

Flörke, U.; Ahmida, A.; Schröder, J.; Egold, H.; Henkel, G.

doi:10.1107/S1600536813006879

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page m211

doi:10.1107/S1600536813006879

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Dichloridobis(1,3-diisopropyl-4,5-dimethyl-1H-imidazol-3-ium-2-thiolate-κS)copper(II)

Ulrich Flörke,^a ^* Aziza Ahmida,^a Jörg Schröder,^a Hans Egold ^a and Gerald Henkel ^a

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

(Received 6 March 2013; accepted 12 March 2013; online 16 March 2013)

The molecular structure of the title compound, [CuCl₂(C₁₁H₂₀N₂S)₂], shows the Cu^II atom with a distorted tetrahedral geometry from two Cl atoms [Cu—Cl = 2.2182 (6) Å] and two thione S atoms [Cu—S = 2.3199 (6) Å]. The angles at the copper cation, which lies on a twofold rotation axis, are Cl—Cu—Cl = 142.84 (4)°, Cl—Cu—S = 94.80 (2) and 99.97 (2)°, and S—Cu—S = 132.46 (4)°. The planes of the two imidazolium rings make a dihedral angle of 76.92 (8)°.

Related literature

For structures of related compounds, see: Griffith et al. (1978 ); Kuhn et al. (1996 ).

Experimental

Crystal data

[CuCl₂(C₁₁H₂₀N₂S)₂]
M_r = 559.14
Orthorhombic, P b c n
a = 14.0663 (12) Å
b = 13.1359 (11) Å
c = 14.9278 (13) Å
V = 2758.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 120 K
0.45 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.846, T_max = 0.991
26735 measured reflections
3418 independent reflections
2575 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.104
S = 1.07
3418 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813006879/nc2307sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006879/nc2307Isup2.hkl

checkCIF report

Related literature top

For structures of related compounds, see: Griffith et al. (1978); Kuhn et al. (1996).

Experimental top

To a solution of 1,3-diisopropyl-4,5-dimethylimidazoline-2-thione (0.584 mg, 2.75 mmol) in acetonitrile (40 ml) CuCl₂ H₂O (0.168 mg, 1.25 mmol) was added and the mixture was stirred at room temperature for 48 h. Afterwards the solvent was removed under vacuum. Blue crystals were obtained from an acetonitrile solution by diethyl ether diffusion.

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

Fig. 1. Molecular structure of the title compound with labeling. Displacement ellipsoids are drawn at the 50% probability level.

Dichloridobis(1,3-diisopropyl-4,5-dimethyl-1H-imidazol-3-ium-2-thiolate-κS)copper(II) top

Crystal data top

[CuCl₂(C₁₁H₂₀N₂S)₂]	F(000) = 1180
M_r = 559.14	D_x = 1.346 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2598 reflections
a = 14.0663 (12) Å	θ = 2.5–22.4°
b = 13.1359 (11) Å	µ = 1.15 mm⁻¹
c = 14.9278 (13) Å	T = 120 K
V = 2758.3 (4) Å³	Prism, blue
Z = 4	0.45 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3418 independent reflections
Radiation source: sealed tube	2575 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ϕ and ω scans	θ_max = 28.2°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −17→18
T_min = 0.846, T_max = 0.991	k = −17→17
26735 measured reflections	l = −19→19

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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F²) = 0.104	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.052P)²] where P = (F_o² + 2F_c²)/3
3418 reflections	(Δ/σ)_max = 0.001
147 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[CuCl₂(C₁₁H₂₀N₂S)₂]	V = 2758.3 (4) Å³
M_r = 559.14	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.0663 (12) Å	µ = 1.15 mm⁻¹
b = 13.1359 (11) Å	T = 120 K
c = 14.9278 (13) Å	0.45 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3418 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2575 reflections with I > 2σ(I)
T_min = 0.846, T_max = 0.991	R_int = 0.055
26735 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.07	Δρ_max = 0.52 e Å⁻³
3418 reflections	Δρ_min = −0.32 e Å⁻³
147 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
Cu1	0.5000	0.67838 (3)	0.7500	0.02220 (13)
Cl1	0.63711 (4)	0.62457 (5)	0.80610 (4)	0.03363 (17)
S1	0.56717 (4)	0.74956 (5)	0.62263 (4)	0.02594 (16)
N1	0.44956 (13)	0.73957 (15)	0.47742 (12)	0.0214 (4)
N2	0.41116 (13)	0.86096 (15)	0.56948 (12)	0.0232 (4)
C1	0.47271 (16)	0.78364 (18)	0.55592 (15)	0.0218 (5)
C2	0.50291 (16)	0.65185 (18)	0.44065 (16)	0.0254 (5)
H2A	0.5421	0.6239	0.4908	0.030*
C3	0.4384 (2)	0.5668 (2)	0.4097 (2)	0.0435 (7)
H3A	0.3913	0.5522	0.4564	0.065*
H3B	0.4763	0.5056	0.3980	0.065*
H3C	0.4057	0.5875	0.3547	0.065*
C4	0.57176 (19)	0.6862 (2)	0.36847 (18)	0.0361 (6)
H4A	0.5367	0.7215	0.3210	0.054*
H4B	0.6042	0.6267	0.3432	0.054*
H4C	0.6188	0.7325	0.3946	0.054*
C5	0.37268 (16)	0.7910 (2)	0.44012 (15)	0.0255 (5)
C6	0.32782 (19)	0.7665 (2)	0.35256 (16)	0.0375 (7)
H6A	0.2844	0.8215	0.3355	0.056*
H6B	0.2922	0.7026	0.3577	0.056*
H6C	0.3773	0.7592	0.3068	0.056*
C7	0.34874 (16)	0.86563 (19)	0.49766 (16)	0.0261 (5)
C8	0.27223 (19)	0.9433 (2)	0.48648 (18)	0.0379 (7)
H8A	0.3010	1.0100	0.4752	0.057*
H8B	0.2338	0.9464	0.5412	0.057*
H8C	0.2317	0.9244	0.4357	0.057*
C9	0.41332 (18)	0.92589 (19)	0.64987 (15)	0.0279 (5)
H9A	0.4665	0.9003	0.6882	0.033*
C10	0.4372 (3)	1.0351 (2)	0.6261 (2)	0.0581 (9)
H10A	0.4944	1.0365	0.5887	0.087*
H10B	0.4486	1.0739	0.6811	0.087*
H10C	0.3840	1.0654	0.5932	0.087*
C11	0.32354 (18)	0.9163 (2)	0.70488 (17)	0.0347 (6)
H11A	0.2725	0.9555	0.6765	0.052*
H11B	0.3350	0.9427	0.7653	0.052*
H11C	0.3049	0.8445	0.7085	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0219 (2)	0.0220 (2)	0.0227 (2)	0.000	−0.00117 (16)	0.000
Cl1	0.0280 (3)	0.0363 (4)	0.0366 (3)	0.0100 (3)	−0.0029 (3)	0.0046 (3)
S1	0.0180 (3)	0.0380 (4)	0.0218 (3)	0.0020 (3)	−0.0010 (2)	0.0018 (3)
N1	0.0177 (10)	0.0267 (11)	0.0198 (9)	−0.0028 (8)	0.0009 (7)	0.0018 (8)
N2	0.0184 (10)	0.0283 (11)	0.0229 (9)	−0.0004 (8)	0.0016 (8)	0.0015 (8)
C1	0.0173 (11)	0.0272 (12)	0.0208 (11)	−0.0027 (10)	0.0033 (9)	0.0035 (9)
C2	0.0279 (13)	0.0237 (12)	0.0246 (11)	0.0027 (10)	0.0000 (10)	0.0004 (9)
C3	0.0509 (19)	0.0306 (16)	0.0488 (17)	−0.0065 (13)	−0.0044 (14)	−0.0060 (13)
C4	0.0337 (15)	0.0368 (16)	0.0378 (15)	0.0084 (12)	0.0102 (12)	0.0047 (12)
C5	0.0174 (12)	0.0355 (14)	0.0236 (11)	−0.0019 (10)	−0.0001 (9)	0.0023 (10)
C6	0.0285 (14)	0.0579 (19)	0.0263 (12)	0.0046 (13)	−0.0043 (11)	−0.0051 (12)
C7	0.0197 (12)	0.0344 (15)	0.0242 (11)	0.0005 (10)	−0.0003 (9)	0.0046 (10)
C8	0.0311 (15)	0.0493 (18)	0.0332 (13)	0.0120 (13)	−0.0022 (12)	0.0034 (12)
C9	0.0283 (13)	0.0322 (14)	0.0232 (11)	0.0021 (11)	−0.0006 (10)	−0.0040 (10)
C10	0.088 (3)	0.0421 (19)	0.0439 (17)	−0.0260 (18)	0.0083 (18)	−0.0099 (15)
C11	0.0338 (15)	0.0402 (16)	0.0301 (13)	0.0084 (13)	0.0076 (11)	−0.0034 (11)

Geometric parameters (Å, º) top

Cu1—Cl1ⁱ	2.2182 (6)	C4—H4C	0.9800
Cu1—Cl1	2.2182 (6)	C5—C7	1.346 (3)
Cu1—S1	2.3199 (6)	C5—C6	1.487 (3)
Cu1—S1ⁱ	2.3199 (6)	C6—H6A	0.9800
S1—C1	1.720 (2)	C6—H6B	0.9800
N1—C1	1.347 (3)	C6—H6C	0.9800
N1—C5	1.392 (3)	C7—C8	1.492 (3)
N1—C2	1.481 (3)	C8—H8A	0.9800
N2—C1	1.350 (3)	C8—H8B	0.9800
N2—C7	1.387 (3)	C8—H8C	0.9800
N2—C9	1.472 (3)	C9—C11	1.512 (3)
C2—C3	1.512 (3)	C9—C10	1.515 (4)
C2—C4	1.517 (3)	C9—H9A	1.0000
C2—H2A	1.0000	C10—H10A	0.9800
C3—H3A	0.9800	C10—H10B	0.9800
C3—H3B	0.9800	C10—H10C	0.9800
C3—H3C	0.9800	C11—H11A	0.9800
C4—H4A	0.9800	C11—H11B	0.9800
C4—H4B	0.9800	C11—H11C	0.9800

Cl1ⁱ—Cu1—Cl1	142.84 (4)	C7—C5—C6	127.8 (2)
Cl1ⁱ—Cu1—S1	99.97 (2)	N1—C5—C6	125.2 (2)
Cl1—Cu1—S1	94.80 (2)	C5—C6—H6A	109.5
Cl1ⁱ—Cu1—S1ⁱ	94.80 (2)	C5—C6—H6B	109.5
Cl1—Cu1—S1ⁱ	99.97 (2)	H6A—C6—H6B	109.5
S1—Cu1—S1ⁱ	132.46 (4)	C5—C6—H6C	109.5
C1—S1—Cu1	105.36 (8)	H6A—C6—H6C	109.5
C1—N1—C5	109.10 (19)	H6B—C6—H6C	109.5
C1—N1—C2	122.31 (19)	C5—C7—N2	107.6 (2)
C5—N1—C2	128.57 (19)	C5—C7—C8	127.4 (2)
C1—N2—C7	108.9 (2)	N2—C7—C8	125.0 (2)
C1—N2—C9	123.01 (19)	C7—C8—H8A	109.5
C7—N2—C9	128.1 (2)	C7—C8—H8B	109.5
N1—C1—N2	107.4 (2)	H8A—C8—H8B	109.5
N1—C1—S1	125.36 (18)	C7—C8—H8C	109.5
N2—C1—S1	127.19 (18)	H8A—C8—H8C	109.5
N1—C2—C3	112.6 (2)	H8B—C8—H8C	109.5
N1—C2—C4	110.8 (2)	N2—C9—C11	112.2 (2)
C3—C2—C4	112.7 (2)	N2—C9—C10	111.2 (2)
N1—C2—H2A	106.8	C11—C9—C10	113.0 (2)
C3—C2—H2A	106.8	N2—C9—H9A	106.6
C4—C2—H2A	106.8	C11—C9—H9A	106.6
C2—C3—H3A	109.5	C10—C9—H9A	106.6
C2—C3—H3B	109.5	C9—C10—H10A	109.5
H3A—C3—H3B	109.5	C9—C10—H10B	109.5
C2—C3—H3C	109.5	H10A—C10—H10B	109.5
H3A—C3—H3C	109.5	C9—C10—H10C	109.5
H3B—C3—H3C	109.5	H10A—C10—H10C	109.5
C2—C4—H4A	109.5	H10B—C10—H10C	109.5
C2—C4—H4B	109.5	C9—C11—H11A	109.5
H4A—C4—H4B	109.5	C9—C11—H11B	109.5
C2—C4—H4C	109.5	H11A—C11—H11B	109.5
H4A—C4—H4C	109.5	C9—C11—H11C	109.5
H4B—C4—H4C	109.5	H11A—C11—H11C	109.5
C7—C5—N1	107.0 (2)	H11B—C11—H11C	109.5

Cl1ⁱ—Cu1—S1—C1	26.05 (9)	C1—N1—C5—C7	−1.0 (3)
Cl1—Cu1—S1—C1	171.81 (9)	C2—N1—C5—C7	−179.6 (2)
S1ⁱ—Cu1—S1—C1	−79.98 (9)	C1—N1—C5—C6	178.6 (2)
C5—N1—C1—N2	0.8 (2)	C2—N1—C5—C6	0.0 (4)
C2—N1—C1—N2	179.55 (19)	N1—C5—C7—N2	0.7 (3)
C5—N1—C1—S1	−176.49 (17)	C6—C5—C7—N2	−178.8 (2)
C2—N1—C1—S1	2.2 (3)	N1—C5—C7—C8	178.2 (2)
C7—N2—C1—N1	−0.4 (3)	C6—C5—C7—C8	−1.3 (4)
C9—N2—C1—N1	178.81 (19)	C1—N2—C7—C5	−0.2 (3)
C7—N2—C1—S1	176.86 (17)	C9—N2—C7—C5	−179.4 (2)
C9—N2—C1—S1	−3.9 (3)	C1—N2—C7—C8	−177.8 (2)
Cu1—S1—C1—N1	−111.48 (19)	C9—N2—C7—C8	3.0 (4)
Cu1—S1—C1—N2	71.7 (2)	C1—N2—C9—C11	−116.7 (2)
C1—N1—C2—C3	132.1 (2)	C7—N2—C9—C11	62.3 (3)
C5—N1—C2—C3	−49.4 (3)	C1—N2—C9—C10	115.6 (3)
C1—N1—C2—C4	−100.6 (2)	C7—N2—C9—C10	−65.3 (3)
C5—N1—C2—C4	77.8 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₁H₂₀N₂S)₂]
M_r	559.14
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	120
a, b, c (Å)	14.0663 (12), 13.1359 (11), 14.9278 (13)
V (Å³)	2758.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.45 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.846, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	26735, 3418, 2575
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.104, 1.07
No. of reflections	3418
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.32

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

References

Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Griffith, E. A. H., Spofford, W. A. III & Amma, E. L. (1978). Inorg. Chem. 17, 1913–1917. CSD CrossRef CAS Web of Science Google Scholar
Kuhn, N., Fawzi, R., Kratz, T., Steimann, M. & Henkel, G. (1996). Phosphorus Sulfur Silicon, 108, 107–119. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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