The reaction of copper( I) iodide with 1, 3-imidazolidine-2-thione (SC3H6N2) in a 1: 2 molar ratio (M/L) has formed unusual 1D polymers, {Cu-6(mu(3)-SC3H6N2)(4)(mu-SC3H6N2)(2)(mu-I)(2)I-4}(n) (1) and {Cu6(mu 3-SC3H6N2)(2)(mu-SC3H6N2)(4)(mu-I)(4)I-2}(n) (1a). A similar reaction with copper(I) bromide has formed a polymer {Cu-6(mu(3)-SC3H6N2)(2)(mu-SC3H6N2)(4)(mu-Br)(4)Br-2}(n) (3a), similar to 1a, along with a dimer, {Cu-2(mu-SC3H6N2)(2)(eta(1)-SC3H6N2)(2)Br-2} (3). Copper(I) chloride behaved differently, and only an unsymmetrical dimer, {Cu-2(mu-SC3H6N2)(eta 1-SC3H6N2)(3)Cl-2} (4), was formed. Finally, reactions of copper(I) thiocyanate in 1:1 or 1:2 molar ratios yielded a 3D polymer, {Cu-2(mu-SC3H6N2)(2)(mu-SCN)(2)}(n) (2). Crystal data: 1, C9H18Cu3I3N6S3, triclinic, P (1) over bar, a = 9.6646(11) angstrom, b = 10.5520(13) angstrom, c = 12.6177(15) angstrom, alpha = 107.239(2)degrees, beta = 99.844(2)degrees, gamma = 113.682(2)degrees, V = 1061.8(2) angstrom(3), Z = 2, R = 0.0333; 2, C4H6CuN3S2, monoclinic, P2(1)/c, a = 7.864(3) angstrom, b) 14.328(6) angstrom, c = 6.737(2) angstrom, beta = 100.07(3)degrees, V = 747.4(5), Z = 4, R = 0.0363; 3, C12H24Br2Cu2N8S4, monoclinic, C2/c, a = 19.420(7) angstrom, b = 7.686(3) angstrom, c = 16.706(6) angstrom, beta = 115.844(6), V = 2244.1(14) angstrom(3), Z = 4, R = 0.0228; 4, C12H24Cl2Cu2N8S4, monoclinic, P2(1)/c, a = 7.4500(6) angstrom, b = 18.4965(15) angstrom, c = 16.2131 (14) angstrom, beta = 95.036(2)degrees, V = 2225.5(3) angstrom(3), Z = 4, R = 0.0392. The 3D polymer 2 exhibits 20-membered metallacyclic rings in its structure, while synthesis of linear polymers, 1 and 1a, represents an unusual example of I (1a)-S (1) bond isomerism.