Versatile coordination patterns in the reaction system of N-benzoyl-N'-(2-2-pyridyl) thiourea with CuCl_2. Their reaction conditions, systematic isolation and crystal structures

摘要

A versatile reaction system; N-benzoyl-N'-(2-pyridyl)thiourea (L) with CuCl_2, has been studied under conditions of control of the relative concentration of the components (L or CuCl_2). Therefore, both converse approaches were employed: one is dropwise addition of L to CuCl_2 in ethanol solution, from which a dark-brown needle-like crystal, infinity~1{[CuClL'][Cl]} 1, was obtained, which is a chloride-bridged one-dimensional Cu(II) polynuclear complex coordinated by the oxidative cyclization product L' generated from L (L'=2-benzoylimino-[1,2,4]thiadiazolo-[2,3-a]pyridine), and the second approach is conversely dropping CuCl_2 into L in acetone solution; at first, a pale-yellow reduced copper(I) mononuclear complex, [CuL_2Cl] 2, was formed, which exhibits a planar molecular configuration with a reguar three coordination geometry, and then a red bis-sulfur-bridged copper(II) dinuclear complex, {[CuLCl_2]_2} 3, appeared subsequently. The crystal structures of these three products have been determined by X-ray diffraction. From the presented results the coordination and redox reaction pathways in the L-CuCl_2 system have been clearly revealed.