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Two novel cyano-bridged heteropolynuclear complexes, [Zn(mprd) 2 Ni(l-CN) 4 ] n (1) and {[Cd(mprd) 2 Ni (l-CN) 4 ]Á2H 2 O} n (2), (mprd = 4-methylpyrimidine), have been synthesized and characterized by FT-IR spectroscopy, Raman spectroscopy, thermal analyses (TG, DTG and DTA) and elemental analyses. The crystal structure of the 1 was determined by X-ray single crystal diffraction. The complex crystallizes in the monoclinic, space group C2/c. The crystal structure of 1 consists of a corrugated 2D network in which the Zn(II) and Ni(II) atoms are linked by cyanide groups. The Ni(II) atom is four coordinate with four carbon atoms in a square-planar geometry; and, the Zn(II) atom is six coordinate with four cyanide-nitrogen and two mprd-nitrogen atoms with a distorted octahedral geometry. The shifts of the cyano stretching vibration are evidence for the formation of cyano bridges. Vibration assignments are given for all the observed bands and the spectral features support the structure of the polymeric complexes.

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ABSTRACT. Three new cyano-bridged heteronuclear polymeric complexes, [Cu(etim) 2-coordinated to the adjacent M(II) ions and three nitrogen atoms of the etim ligands. The Cd(II) ion of the Cd-Ni-etim complex is six-coordinate, completed with the two nitrogen atoms of the etim ligands and the four nitrogen atoms from bridging cyano groups. Polymeric structures of the Cu-Ni-etim and the Zn-Ni-etim complexes are 1D coordination polymer, while complex the Cd-Ni-etim presents a 2D network. The thermal decompositions in the temperature range 30-700 C of the complexes were investigated in the static air atmosphere.

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