Synthesis and structure of coordination polymers of Mn2+, Cu2+, Ag+, Zn2+ and Cd2+ by combination of bipyrazole and diphenate ligands

Five new coordination polymers, [Mn(DPA)(Me4bpz)(H2O)](I)∞1, [Cu(DPA)(Me4bpz)2]·H2O(II)∞1, [Ag4(OAc)2(Me4bpz)3(H2O)1.56](III)∞2, [Zn(DPA)(Me4bpz)]·0.61H2O(IV)∞3 and [Cd(DPA)(Me4bpz)](V)∞3[DPA: diphenic acid dianion, OAc: acetate, Me4bpz: 3,3′,5,5′-tetramethyl-4,4′-bipyrazole], were obtained from acetate hydrates of Mn2+, Cu2+, Ag+, Zn2+ and Cd2+ and a mixed ligand system consisting of Me4bpz and diphenic acid by hydrothermal synthesis under similar conditions. Their crystal structures were determined by means of X-ray single crystal structure analysis. Furthermore, the compounds were characterized by means of elemental analysis and IR spectroscopy. The polymers I and II exhibit one-dimensional chain structures with only one type of bridging ligand, whereas the polymers IV and V realize three-dimensional coordination frameworks with diamond topology involving both ligand types as bridging ligands. Compound III contains a two-dimensional cationic framework which is charge compensated by acetate anions. The coordination environments of the metal centers are predominant directly supported by N–H ⋯ O hydrogen bonds providing further evidence for the bipyrazole-carboxylate supramolecular synthon.

Five new coordination polymers were obtained from the acetate hydrates of Mn2+, Cu2+, Ag+, Zn2+ and Cd2+ and a mixed ligand system consisting of Me4bpz and diphenic acid by hydrothermal synthesis under similar conditions. Their crystal structures were determined by means of X-ray single crystal structure analysis. The polymers I and II exhibit one-dimensional chain structures, whereas the polymers IV and V realize three-dimensional coordination frameworks. Compound III contains a two-dimensional cationic framework. The coordination environments of the metal centers are predominant directly supported by N–H ⋯ O hydrogen bonds providing further evidence for the bipyrazole-carboxylate supramolecular synthon.Figure optionsDownload as PowerPoint slideHighlights
► Five new mixed ligand coordination polymers were obtained by hydrothermal synthesis.
► Two polymers at a time exhibit 1D chain structures and 3D coordination frameworks.
► The environments of the metal ions are predominant supported by N–H ⋯ O hydrogen bonds.
► Further evidence for the bipyrazole-carboxylate supramolecular synthon is provided.