Polymeric Octahedral and Monomeric Tetrahedral Group 12 Pseudohalogeno (NCX-: X = O, S, Se) Complexes of 4-(N,N-dimethylamino)pyridine
A series of new pseudohalogeno complexes of Zn(II), Cd(II) and Hg(II) with 4-(N,N-dimethylamino)pyridine (4-dmap) has been prepared. The compounds Zn(NCS)2L2 (1), Cd(NCS)2L2 (2a), Hg1.5(NCS)3L2 (3), Zn(NCO)2L2 (4), Cd(NCO)2L2 (5), Hg(NCO)2L (6), Zn(NCSe)2L2 (7) and Cd(NCSe)2L2 (8a) (L = 4-dmap) were characterized by elemental analyses, mid and far IR, 1H and 13C NMR spectroscopy, and differential scanning calorimetry. The structures of 1, 2a, 4 and 8a have been confirmed by X-ray crystallography. In addition, molecular geometries of Cd(NCS)2L2·2DMSO (2b) and Cd(NCSe)2L2·2DMSO (8b) have been determined by X-ray crystallography. Compounds 1 and 4 consist of monomeric units in which the Zn(II) atoms are tetrahedrally surrounded by two N-donating pseudohalide ions and two 4-dmap moities, coordinating at the endocyclic nitrogen atom. Complexes 2a and 8a are isostructural polymers comprised of chains of the monomeric unit MX2N2, where X is NCS- or NCSe-. Within each monomeric unit one pseudohalide ligand is bound through the chalcogen atom; the other through the nitrogen atom. The polymer chain is a distorted octahedron sharing common edges through nearly linear bridging pseudohalide groups displaced trans to each other; the two 4-dmap ligands are also displaced trans to each other. Complexes 2b and 8b are isostructural monomeric units, in which the central Cd(II) atom exhibits an N4O2 octahedral geometry.
P. M. Secondo et al., "Polymeric Octahedral and Monomeric Tetrahedral Group 12 Pseudohalogeno (NCX-: X = O, S, Se) Complexes of 4-(N,N-dimethylamino)pyridine," Inorganica Chimica Acta, Elsevier, Nov 2000.
The definitive version is available at http://dx.doi.org/10.1016/S0020-1693(00)00224-3
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