Synthesis and structure of coordination polymers of Mn~(2+), Cu~(2+), Ag~+, Zn~(2+) and Cd~(2+) by combination of bipyrazole and diphenate ligands

摘要

Five new coordination polymers, [Mn(DPA)(~(Me4)bpz)(~(H2)O)](I)_1, [Cu(DPA)(~(Me4)bpz)_2] ·~(H2)O(II)_1 [~(Ag4)(OAc)_2(~(Me4)bpz)_3(~(H2)O)_(1.56)](III) _2, [Zn(DPA)(~(Me4)bpz)]·0.61~(H2)O(IV) _3 and [Cd(DPA)(~(Me4)bpz)](V)_3[DPA: diphenic acid dianion, OAc: acetate, Me_4bpz: 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.