Coordination Mode of the Zinc( II ) and Cadmium( II ) Cations with N ‐(Diisopropoxyphosphoryl)thiobenzamide

Reaction of the potassium salt of N ‐(diisopropoxyphosphoryl)thiobenzamide ( i PrO) 2 P(O)NHC(S)C 6 H 5 ( HL ) with Zn II and Cd II cations in aqueous EtOH leads to three different complexes: [Zn(L‐ O , S ) 2 ] ( 1 ), [Cd 2 (L‐ O , S ) 4 ] ( 2 ) and [Cd(HL‐ O ) 2 (L‐ O , S ) 2 ] ( 3 ). The structures of these compounds were investigated by single‐crystal X‐ray diffraction analysis, EI‐MS and ES‐MS, IR, 1 H, 13 C and 31 P NMR spectroscopy and microanalysis. The zinc( II ) atom in complex 1 is in a distorted tetrahedral ZnO 2 S 2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. The cadmium( II ) complex 2 is centrosymmetric and consists of dimeric species. Two [Cd(L‐ O , S ) 2 ] moieties are connected by two bridging [S–Cd–S] units through the sulfur atoms of the ligand C=S groups. Complex 2 has a distorted trigonal‐bipyramidal Cd(O ax ) 2 (S eq ) 3 core. Complex 3 has a tetragonal‐bipyramidal environment, Cd(O ax ) 2 (O eq ) 2 (S eq ) 2 , and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in a typical 1,5‐O,S coordination mode. The ligands are in a trans configuration. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)