Abstract
Reaction of copper(I) chloride with 1,3-imidazoline-2-thione (imzSH) in the presence of Ph 3P in 1:2:2 or 1:1:2 (M:L:PPh 3) molar ratios yielded a compound of unusual composition, [Cu 2(imzSH)(PPh 3) 4Cl 2] · CH 3OH ( 1), whose X-ray crystallography has shown that its crystals consist of four coordinated [CuCl(1κS-imzSH)(PPh 3) 2] ( 1a), and three coordinated [Cu(PPh 3) 2Cl] ( 1b) independent molecules in the same unit cell. In contrast, crystals of complexes of copper(I) bromide/iodide are formed by single molecules of [CuBr(1κS-imzSH)(PPh 3) 2] · H 2O ( 2) and [CuI(1κS-imzSH)(PPh 3) 2] ( 3), respectively, similar to molecule 1a. The related ligand, 1,3-benzimidazoline-2-thione (bzimSH) formed a complex [CuBr(1κS-bzimSH)(PPh 3) 2] · CH 3COCH 3 ( 4), similar to 2. The formation of 1a and 1b has been also revealed by NMR spectroscopy. The NMR spectra of 2– 4 also showed weak signals indicating formation of compounds similar to 1b. It reveals that the lability of the Cu–S bond varies in the order: Cl ≫ Br ∼ I. Weak interactions {e.g. C–H⋯π electrons of ring, –NH⋯halogens/oxygen, C–H⋯halogens/oxygen, π⋯π (between rings)} have played an important role in building 2D chains of complexes 1– 4.
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