Synthesis and Characterization of Copper(I) Halide Complexes with Thiourea and Heterocyclic Thione

Reactions of N,N'-diisopropyl-thiourea (abbreviated as L-1) with CuCl2 and CuBr2 afforded the trimeric ((LCuCl)-Cu-1)(3) (1) and ((LCuBr)-Cu-1)(3) (2), respectively, featuring the sulfur bridged Cu3S3 six-membered ring each as the core structure. During the reaction, Cu(II) was reduced to Cu(I). Similarly, the reactions of L-1 with CuCl and CuBr gave the same products as those by L-1 with respective CuCl2 and CuBr2. In contrast, treatment of 1,3-diisopropyl-4,5-dimethylimidazole-2(3H)-thione (L-2) with Culled to the formation of sulfur and iodide mixed-bridged complex [(L-2)(4)(CuI)(5)] (3), in which two co-vertice Cu3S2I six-membered rings were fused by an iodide atom. Compounds obtained were characterized by H-1 NMR and C-13 spectroscopy, elemental analysis, and single-crystal X-ray diffraction. 2 belongs to the monoclinic system, space group P2(1)/c with a = 19.6009(10), b = 11.5069(6), c = 17.1744(9) angstrom, beta = 109.062(3)degrees, V = 3661.2(3) angstrom(3), C21H48Br3Cu3N6S3, M-r= 911.18, Z= 4, D-c= 1.653 Mg/m(3), mu(MoK alpha) = 5.192 mm(-1), F(000) = 1824, S = 1.030, the final R = 0.0374 and wR = 0.0808 for 4988 observed reflections (I> 2 sigma(I)) and R = 0.0726 and wR = 0.0916 for all data. 3.2THF belongs to the monoclinic system, space group I2/a with a = 19.7335(6), b = 13.3544(4), c = 29.6355(11) angstrom, beta = 105.415(2)degrees, V = 7528.9(4) angstrom(3), C52H96Cu5I5N8O2S4, M-r= 1945.81, Z= 4, D-c= 1.717 Mg/m(3), mu(MoK alpha) = 3.589 mm(-1), F(000) = 3816, S = 1.034, the final R = 0.0325 and wR = 0.0810 for 5704 observed reflections (I> 2 sigma(I)) and R = 0.0447 and wR = 0.0910 for all data.