Crystal structure of bis­[1,3,4,5-tetra­methyl-1H-imidazole-2(3H)-thione-κS]chlorido­copper(I)

Ulrich Flörke; Aziza Ahmida; Hans Egold; Gerald Henkel

doi:10.1107/S1600536814024404

. 2014 Nov 15;70(Pt 12):m397–m398. doi: 10.1107/S1600536814024404

Crystal structure of bis[1,3,4,5-tetramethyl-1H-imidazole-2(3H)-thione-κS]chloridocopper(I)

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

PMCID: PMC4257435 PMID: 25553008

Abstract

The molecular structure of the title compound, [CuCl(C₇H₁₂N₂S)₂], shows a slightly distorted trigonal–planar coordination geometry of the Cu atom. The Cu—Cl bond measures 2.2287 (9) Å, and the two Cu—S bonds are significantly different from each other, with values of 2.2270 (10) and 2.2662 (10) Å. Also, the S—Cu—Cl angles differ, with values of 113.80 (4) and 124.42 (4)°, while the S—Cu—S angle is 121.51 (4)°. The two imidazole rings are almost parallel, making a dihedral angle of 2.1 (2)°. In the crystal, the shortest C—H⋯Cl interactions stabilize a three-dimensional network with molecules linked into centrosymmetric dimers that are stacked along the b-axis direction.

Keywords: crystal structure, trigonal coordination, copper, imidazole

Related literature

For structures of related Cu complexes, see: Devillanova et al. (1980 ▶); Kimani et al. (2011 ▶). For background to effective anti-oxidants, see: Bhabak et al. (2010 ▶); Yamashita & Yamashita (2010 ▶).

Experimental

Crystal data

[CuCl(C₇H₁₂N₂S)₂]
M _r = 411.48
Monoclinic,
a = 9.4738 (14) Å
b = 13.662 (2) Å
c = 14.119 (2) Å
β = 98.314 (3)°
V = 1808.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.59 mm⁻¹
T = 120 K
0.25 × 0.20 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.692, T _max = 0.845
17386 measured reflections
4304 independent reflections
2584 reflections with I > 2σ(I)
R _int = 0.099

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.091
S = 0.85
4304 reflections
207 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.58 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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814024404/zq2228sup1.cif

e-70-0m397-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814024404/zq2228Isup2.hkl

e-70-0m397-Isup2.hkl^{(210.9KB, hkl)}

Click here for additional data file.^{(465KB, tif)}

. DOI: 10.1107/S1600536814024404/zq2228fig1.tif

Molecular structure of the title compound with anisotropic displacement parameters drawn at the 50% probability level.

CCDC reference: 1032971

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C4H4BCl1ⁱ	0.98	2.75	3.717(4)	170
C11H11ACl1ⁱⁱ	0.98	2.76	3.721(3)	165
C14H14BCl1ⁱⁱⁱ	0.98	2.80	3.782(4)	176

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

supplementary crystallographic information

S1. Comment

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). Here we report the synthesis of a copper(I) chloride complex with 1,3,4,5-tetra-methylimidazole-2-thione ligands.

The title compound shows the same trans configuration as the bis-N,N'-dimethylimidazole-thione-Cu(I) compound (Kimani et al., 2011) or bis-N,N'-dimethylimidazolidine-thione-CuCl (Devillanova et al., 1980) whereas the cis configuration is also known for bis-N,N'-dimethylimidazole-thione-CuX (X = Cl, Br, I) (Kimani et al., 2011). In contrast to all the reported complexes in the title compound both Cu and Cl atoms lie on general positions and the two Cu—S bond lengths differ strongly with Cu–S1 2.2662 (10) and Cu–S2 2.2270 (10) Å. Also the S—Cu—Cl angles differ with 113.80 (4)° and 124.41 (4)°, while the S—Cu—S angle is 121.51 (4)°.

The intramolecular hydrogen bonds between the chlorine atom and hydrogen atoms of the methyl group amount to 4.838 (H2b—Cl) and 4.911 Å(H9a—Cl).

S2. Experimental

To a solution of 1,3,4,5-tetra-methylimidazoline-2-thione (0.390 mg, 2.75 mmol) in acetonitrile (50 ml) CuCl₂ (0.168 mg, 1.25 mmol) was added and the mixture was stirred at room temperature for 24 h. Afterwards the solvent was removed under vacuum. White crystals were obtained from diffusion of diethyl ether into acetonitrile.