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.

Vibrational–Structural Combined Study into Luminescent Mixed Copper(I)/Copper(II) Cyanide Coordination Polymers

“…[9][10][11][12][13][14][15][16][17][18][19] A wide range of Cu I compounds have been prepared with various organic ligands. [20] Different luminescence pathways have been detected and studied thoroughly to correlate metalto-ligand charge transfer, which can give rise to variations in emission range and quantum yields. On the other hand, the rational design and preparation of mixed-valence Cu I /Cu II coordination complexes, which are of great biological importance and display interesting electronic properties, is still a challenge.…”

catena-Poly[[[bis(thiourea-κS)copper(I)]-μ-thiourea-κ2S:S] iodide acetonitrile hemisolvate]

“…Comment Some copper(I) compounds containing thiourea ligands have been described previously (Bombicz et al, 2004;Bott et al, 1998;Stocker et al, 1996). In this paper, we report the synthesis and the structure of a complex formed by the reaction of thiourea with cuprous iodide.…”

Linear polymer of a copper(II) complex and its supramolecular selectivity

“…The distance between neighboring Cu(II) ions is short at 2.6440(2) Å ; this is the minimum in all similar structures [21][22][23][24][25][26][27][28][29]. All the Cu(II) ions along the c-axis are arranged on a line to form a linear chain structure (figure 1), but a metal bond can't exist in the title complex because the Cu(II)-Cu(II) length is out of the range for Cu-Cu metal bonds.…”