摘要: Reactions of N,N'-diisopropyl-thiourea (abbreviated as L¹) with CuCl₂ and CuBr₂ afforded the trimeric (L¹CuCl)₃ (1) and (L¹CuBr)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 CuCl and CuBr gave the same products as those by L¹ with respective CuCl₂ and CuBr₂. In contrast, treatment of 1,3-diisopropyl-4,5-dimethylimidazole-2(3H)-thione (L²) with CuI led to the formation of sulfur and iodide mixed-bridged complex [(L²)₄(CuI)₅] (3), in which two co-vertice Cu₃S₂I six-membered rings were fused by an iodide atom. Compounds obtained were characterized by ¹H NMR and ¹³C 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) Å, β=109.062(3)°, V=3661.2(3) ų, C₂₁H₄₈Br₃Cu₃N₆S₃, M_r=911.18, Z=4, D_c=1.653 Mg/m³, μ(MoKα)=5.192 mm^-1, F(000)=1824, S=1.030, the final R=0.0374 and wR=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 P2₁/c with a=19.7335(6), b=13.3544(4), c=29.6355(11) Å, β=105.415(2)°, V=7528.9(4) ų, C₅₂H₉₆Cu₅I₅N₈O₂S₄, M_r=1945.81, Z=4, D_c=1.717 Mg/m³, μ(MoKα)=3.589 mm^-1, F(000)=3816, S=1.034, the final R=0.0325 and wR=0.0810 for 5704 observed reflections (I>2σ(I)) and R=0.0447 and wR=0.0910 for all data.