Four new coordination polymers involving transition metals with 1,2,4,5-benzenetetracarboxylate and pyridyl-donor ligand di(4-pyridyl) sulfide

Four new coordination polymers namely {[Mn2(BT)(DPS)2(H2O)6]·10H2O}n (MnBTDPS), {[Co2(BT)(DPS)2(H2O)6]·10H2O}n (CoBTDPS), {[Cu2(BT)(DPS)(H2O)4]·5H2O}n (CuBTDPS) and {[Zn2(BT)(DPS)2]·6H2O}n (ZnBTDPS), where BT = 1,2,4,5-benzenetetracarboxylate and DPS = di(4-pyridyl) sulfide, were synthesized and characterized by thermal analysis, vibrational spectroscopy (Raman and infrared) and single crystal X-ray diffraction analysis. In all compounds, the DPS ligands are coordinated to metal sites in a bridging mode and the carboxylate moiety of BT ligands adopts a monodentate coordination mode, as indicated by the Raman spectra data through the Δν (νasym(COO) − ν sym(COO)) value. According to X-ray diffraction analysis, MnBTDPS and CoBTDPS are isostructural and in these cases, the metal centers exhibit a distorted octahedral geometry. In CuBTBPP, the Cu2+ centers geometries are best described as square-pyramids, according to the trigonality index τ = 0.14 for Cu1 and τ = 0.10 for Cu2. On the other hand, in ZnBTDPS, the Zn2+ sites adopt a tetrahedral geometry. Finally, the four compounds formed two-dimensional sheets that are connected to each other through hydrogen bonding giving rise to three-dimensional supramolecular arrays.