Reactions of copper(I) halides with imidazolidine-2-thione and 1-methyl-1,3-imidazoline-2-thione in dmso involved C-S rupture in aerobic conditions and yielded a sulfate bridged polymer, [Cu(II){eta(2)-N,N-(N(2)C(3)H(5))(2)S}(mu-O,OSO(2))(eta(1)-OH(2))](n) 1 and a sulfate chelated monomer, [Cu(II){eta(2)-N,N-(N(2)C(4)H(5))(2)S}(eta(2)-O,OSO(2))(eta(1)-OH(2))] 2 {N,N-(N(2)C(3)H(5))(2)S = 2,2'-thio-di-2-imidazoline, N,N-(N(2)C(4)H(5))(2)S = 1,1'-dimethyl-2,2'-di-imidazolyl sulfide}. This variable coordination behavior of in situ generated sulfate is unprecedented in the literature.