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

Reactions of N,N?-diisopropyl-thiourea(abbreviated as L1) with CuC l2 and Cu Br2 afforded the trimeric(L1Cu Cl)3(1) and(L1Cu Br)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 L1 with Cu Cl and Cu Br gave the same products as those by L1 with respective Cu Cl2 and Cu Br2. In contrast, treatment of 1,3-diisopropyl-4,5-dimethylimidazole-2(3H)-thione(L2) with Cu I led to the formation of sulfur and iodide mixed-bridged complex [(L2)4(Cu I)5](3), in which two co-vertice Cu3S2 I six-membered rings were fused by an iodide atom. Compounds obtained were characterized by 1H NMR and 13 C spectroscopy, elemental analysis, and single-crystal X-ray diffraction. 2 belongs to the monoclinic system, space group P21/c with a = 19.6009(10), b = 11.5069(6), c = 17.1744(9) ?, β = 109.062(3)o, V = 3661.2(3) ?3, C21H48Br3Cu3N6S3, Mr = 911.18, Z = 4, Dc = 1.653 Mg/m3, μ(Mo Kα) = 5.192 mm–1, F(000) = 1824, S = 1.030, the final R = 0.0374 and w R = 0.0808 for 4988 observed reflections(I > 2σ(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) ?, β = 105.415(2)o, V = 7528.9(4) ?3, C52H96Cu5I5N8O2S4, Mr = 1945.81, Z = 4, Dc = 1.717 Mg/m3, μ(Mo Kα) = 3.589 mm–1, F(000) = 3816, S = 1.034, the final R = 0.0325 and w R = 0.0810 for 5704 observed reflections(I > 2σ(I)) and R = 0.0447 and wR = 0.0910 for all data.