Crystal structures of a family of silver cyanide complexes of thiourea andsubstituted thioureas

The syntheses and crystal structures of a family of silver cyanide complexe s of thiourea and substituted thioureas are reported. The sulfur ligands in clude thiourea (tu), 1-methyl-2-thiourea (mtu), 1,3-dimethyl-2-thiourea (dm tu), 1,1,3,3-tetramethyl-2-thiourea (tmtu), and 2-imidazolidinethione (N,N- ethylenethiourea, etu). Synthesis was effected by dissolving AgCN in an aqu eous Solution of ligand. Two different complexes were obtained by the react ion of AgCN with tu. Complex la: (AgCN)(tu), monoclinic, P2(1)/c, a = 9.385 1 (6) Angstrom, 6 = 8.2782 (5) Angstrom, c = 7.1178 (5) Angstrom, beta = 94 .591 (1)degrees, and Z = 4. Complex 1b: (AgCN)(tu)(2), Viclinic. P (1) over bar, a = 7.9485 (14) Angstrom, b = 9.431 (2) Angstrom,c = 12.771 (2) Angst rom, alpha = 85.695 (3)degrees, beta = 81.210 (4)degrees, gamma = 77.987 (2 )degrees, and Z = 4. Complex 2: (AgCN)(mtu), triclinic, P (1) over bar, a = 4.113 (2) Angstrom, b = 9.472 (4) Angstrom, c = 9.679 (4) Angstrom, alpha = 113.918 (5)degrees, beta = 98.188 (6)degrees, gamma = 97.725 (6)degrees, and Z = 2. Complex 3 (AgCN)(2)(dmtu)(2), monoclinic, P2(1)/m, a = 7.1482 (7 ) Angstrom, b = 14.776 (2) Angstrom, c = 7.3366 (7) Angstrom, beta = 92.418 (2)degrees, and Z = 2. Complex 4: (AgCN)(tmtu), orthorhombic, P2(1)2(1)2(1 ), a = 8 821(6) Angstrom, b = 10.209 (2) Angstrom, c = 10.362 (2) Angstrom, and Z = 4. Complex 5: (AgCN)(2)(etu)(2), triclinic, P1, a = 6.8001 (2) Ang strom, b = 8.6154 (1) Angstrom, c = 13.4747 (3) Angstrom, alpha = 71.720 (1 )degrees, beta = 79.906 (1)degrees, gamma = 75.885 (2)degrees, and Z = 2. A ll of the structures involve either one- or two-dimensional polymeric array s held together by bridging S and CN groups. There is, however, no similari ty between any two of the arrays. Four of the five ligands used also form s imilar complexes with CuCN. For one ligand, tmtu, the structures are isomor phous. For the other three, not only are the structures not isomorphous, th e m/n ratio in (MCN)(m)L-n when M is Ag is different from that when M is Cu .