Syntheses and coordination isomerism of heteroleptic divalent-metal (M = Co, Zn) carbazate complexes

Three heteroleptic divalent-metal alkyl-carbazate-thiocyanate complexes, [M(NCS)2(NH2NHCOOR)2] [M = Co and R = CH2CH3 (1); M = Co and R = CH3 (2); M = Zn and R = CH3 (3)], have been prepared and characterized, and their crystal structures determined. In 1, Co(II) adopts a fairly regular centrosymmetric trans-CoO2N4 octahedral geometry arising from its coordination by two N,O-bidentate ethylcarbazate ligands and two trans N-bonded thiocyanates. In isostructural 2 and 3, the metals adopt distorted cis-MO2N4 octahedral geometries arising from two N,O-bidentate methylcarbazate ligands with cis N-bonded thiocyanates. The crystal structures feature N–H⋯O and N–H⋯S interactions. Thermal analysis data show that these compounds begin to decompose at temperatures between 130 and 160 °C. Crystal data: 1, CoC8H16N6O4S2, Mr = 383.32, P21/n (No. 14), a = 5.2599(3) A, b = 7.4209(4) A, c = 20.1948(12) A, β = 94.070(1)°, V = 786.28(8) A3, Z = 2, R(F) = 0.028, wR(F2) = 0.073; 2, CoC6H12N6O4S2, Mr = 355.27, P21/n (No. 14), ...