Thermoanalytical and spectral properties of new rare-earth metal 2-pyrazinecarboxylate hydrates

Summary

New 4f-trivalent lanthanide 2-pyrazinecarboxylate hydrates of composition Ln(pyzCOO)<Subscript>3</Subscript>&middot;3.5H<Subscript>2</Subscript>O, where<Emphasis Type=”Italic”> Ln</Emphasis>=La, Ce, Pr, Nd, Sm and Dy have been isolated from aqueous solution containing the respective metal nitrates and 2-pyrazinecarboxylic acid (HpyzCOO), in 1:3 molar ratios. The complexes have been characterized by analytical, electronic and IR spectroscopic, thermal analysis and X-ray diffraction studies. The OCO<Superscript>-</Superscript> group of 2-pyrazinecarboxylate bridges in both mono and bidentate fashion (&ngr;<Subscript>as(COO)</Subscript>=1612 and 1578 cm<Superscript>-1</Superscript>; &ngr;<Subscript>s(COO)</Subscript>=1423 and 1388 cm<Superscript>-1</Superscript>) as evidenced by IR data. The IR spectra further indicate that coordination takes place through the carboxyl group and the nearest hetero-ring nitrogen atom. The bonding parameters &bgr;, <Emphasis Type=”Italic”>b</Emphasis><Superscript>1/2</Superscript>, &percnt;&dgr; and&#61472; &eegr; have been calculated from the electronic spectral (hypersensitive) bands of Pr(III) and Nd(III) complexes. Both IR and thermal data reveal the presence of a coordinated water and two and a half lattice water molecules in the complexes. It is further substantiated by single crystal X-ray study for the corresponding lanthanum compound. Based on the results obtained, nine coordination is proposed for the lanthanide ions. Simultaneous TG-DTA of the complexes show that they are thermally stable up to 150&deg;C and undergo endothermic (~155 and 250&deg;C) followed by exothermic (~480&deg;C) decompositions to give the respective metal oxides as the final product. The compounds are found to be isostructural as evidenced from X-ray powder patterns.