title: Crystal Structures of a Family of New Copper(I) Cyanide Complexes of Thiourea and Substituted Thioureas.
abstract: The syntheses and crystal structures of the first cyanide, sulfur mixed ligand copper(I) complexes are reported. The first complex of the family was discovered when (CuCN)(3)(C(6)H(12)N(4))(2) (1) (C(6)H(12)N(4) = hexamethylenetetramine) was treated with aqueous thiourea. The sulfur ligands include thiourea (tu), 1,3-dimethyl-2-thiourea (dmtu), 1,3-diethyl-2-thiourea (detu), 1,1,3,3-tetramethyl-2-thiourea (tmtu), and 2-imidazolidinethione (N,N'-ethylenethiourea, etu). Synthesis was effected by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. Complex 2, (CuCN)(2)(tu)(3)(H(2)O), crystallizes in the triclinic space group P&onemacr;with unit cell dimensions a = 7.696(5) Å, b = 9.346(2) Å, c = 10.772(2) Å, alpha = 106.53(2) degrees, beta = 91.11(4) degrees, gamma = 98.42(3) degrees, and Z = 2. Complex 3, (CuCN)(3)(dmtu)(2), crystallizes in the monoclinic space group Cc with unit cell dimensions a = 10.082(3) Å, b = 14.984(5) Å, c = 11.413(3) Å, beta = 104.50(2) degrees, and Z = 4. Complex 4, (CuCN)(2)(detu)(H(2)O), crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 7.969(5) Å, b = 11.559(4) Å, c = 13.736(5) Å, beta = 100.48(4) degrees, and Z = 4. Complex 5, (CuCN)(tmtu) (polymorph a), crystallizes in the orthorhombic space group P2(1)2(1)2(1) with unit cell dimensions a = 8.653(1) Å, b = 9.426(1) Å, c = 11.620(3) Å, and Z = 4. Complex 6, (CuCN)(tmtu) (polymorph b), which has the same connectivity as 5, crystallizes in the triclinic space group P&onemacr; with unit cell dimensions a = 9.660(4) Å, b = 14.202(4) Å, c = 16.03(1) Å, alpha = 101.68(5) degrees, beta = 107.08(6) degrees, gamma = 70.07(2) degrees, and Z = 8. The difference between the polymorphs is that 5 has a zig-zag chain with a repeat unit of two while 6 has a 4-fold helix. Complex 7, (CuCN)(2)(etu), crystallizes in the monoclinic space group P2(1)( )()with unit cell dimensions a = 3.994(2) Å, b = 13.886(3) Å, c = 7.556(1) Å, beta = 97.07(2) degrees, and Z = 2.
authors.affiliation: Departments of Chemistry, Macalester College, St. Paul, Minnesota 55105, and University of Minnesota, Minneapolis, Minnesota 55455.
authors.forename: Fred B.
authors.initials: FB
authors.lastname: Stocker
authors.forename: Melissa A.
authors.initials: MA
authors.lastname: Troester
authors.forename: Doyle
authors.initials: D
authors.lastname: Britton