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The reaction of copper(I) iodide with 1, 3-imidazolidine-2-thione (SC 3H6N2) in a 1:2 molar ratio (M/L) has formed unusual 1D polymers, {Cu6(mu3-SC3H 6N2)4(mu-SC3H6N 2)2(mu-I)2I4}n (1) and {Cu6(mu3-SC3H6N2) 2(mu-SC3H6N2)4(mu-I) 4I2}n (1a). A similar reaction with copper(I) bromide has formed a polymer {Cu6(mu3-SC 3H6N2)2(mu-SC3H 6N2)4(mu-Br)4Br2} n (3a), similar to 1a, along with a dimer, {Cu2(mu- SC3H6N2)2(eta1-SC 3H6N2)2Br2} (3). Copper(I) chloride behaved differently, and only an unsymmetrical dimer, {Cu2(mu-SC3H6N2) (eta1-SC3H6N2)3Cl 2} (4), was formed. Finally, reactions of copper-(I) thiocyanate in 1:1 or 1:2 molar ratios yielded a 3D polymer, {Cu2(mu-SC 3H6N2)2(mu-SCN)2} n (2). Crystal data: 1, C9H18Cu 3I3N6S3, triclinic, P1, a = 9.6646(11) A, b = 10.5520(13) A, c = 12.6177(15) A, alpha = 107.239(2), beta = 99.844(2), gamma = 113.682(2), V = 1061.8(2) A3, Z = 2, R = 0.0333; 2, C4H 6CuN3S2, monoclinic, P21/c, a = 7.864(3) A, b = 14.328(6) A, c = 6.737(2) A, beta = 100.07(3), V = 747.4(5), Z = 4, R = 0.0363; 3, C12H 24Br2Cu2N8S4, monoclinic, C2/c, a = 19.420(7) A, b = 7.686(3) A, c = 16.706(6) A, beta = 115.844(6), V = 2244.1(14) A3, Z = 4, R = 0.0228; 4, C12H24Cl2Cu2N8S 4, monoclinic, P21/c, a = 7,4500(6) A, b = 18.4965(15) A, c = 16.2131(14) A, beta = 95.036(2), V = 2225.5(3) A3, 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.
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Reference：
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”