One-Dimensional Pyrazine Bridged M(II)-Saccharinato Coordination Polymers: Synthesis, Characterization, Crystal Structures and Thermal Studies

Abstract

Three new coordination polymers with a general formula [M(sac)<inf>2</inf>(μ-pyz)(H<inf>2</inf>O)<inf>2</inf>]<inf>n</inf> [M = Mn(II) (1), Fe(II) (2), Co(II) (3), pyz = pyrazine, and sac = saccharinate] have been synthesized and characterized by elemental analyses, IR, UV-VIS, magnetic measurements, thermal analysis techniques and single crystal X-ray diffraction. All three complexes are isomorphous, crystallizing in the triclinic space group P over(1, ̄) (No. 2). Each metal(II) ion in 1-3 is octahedrally coordinated by two sac, two pyz and two aqua ligands. The sac ligands are N-coordinated, while the pyz ligands bridge the metal centers leading to an one-dimensional linear chain structure. Intra-chain M-M separations in complexes 1, 2 and 3 are 7.381(2), 7.259(3) and 7.188(3) Å, respectively. The individual chains are linked into two-dimensional layers by O-H⋯O hydrogen bonds involving the hydrogens of aqua ligands and carbonyl and sulfonyl O atoms of sac ligands. The hydrogen bonded layers are further assembled into three-dimensional supramolecular networks by weak aromatic π⋯π stacking interactions between the phenyl rings of sac ligands or CH⋯π interactions involving pyz. These complexes exhibit similar decomposition characteristics. In the first stages, endothermic removal of the aqua and pyz ligand takes place leading to an intermediate probably in the form of [M(sac)<inf>2</inf>], which undergoes highly exothermic decomposition at higher temperatures to give corresponding metal oxides. © 2007 Elsevier Ltd. All rights reserved.