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

Abstract

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,

• a = 14.0663 (12) Å

• b = 13.1359 (11) Å

• c = 14.9278 (13) Å

• V = 2758.3 (4) ų

• 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[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

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.

Refinement

All Hydrogen atom positions were clearly derived from difference maps, then refined at calculated positions riding on the parent atoms with C—H 0.98 - 1.00 Å and isotropic displacement parameters U_iso(H) = 1.2U_eq(C) or 1.5U_eq(CH₃). All CH₃ hydrogen atoms were allowed to rotate but not to tip.

Figures

Fig. 1.

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

Crystal data

[CuCl2(C11H20N2S)2]	F(000) = 1180
Mr = 559.14	Dx = 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

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

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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F2) = 0.104	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.052P)2] where P = (Fo2 + 2Fc2)/3
3418 reflections	(Δ/σ)max = 0.001
147 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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.