A metal-organic framework with paddle-wheel Zn2(CO2)4 secondary building units and cubane-1,4-dicarboxylic acid linkers

Abstract

A new crystal structure of catena-(bis((µ4-cubane-1,4-dicarboxylato)-(N-methyl-2-pyrrolidone)-zinc(II)) N-methyl-2-pyrrolidone solvate) (1) was prepared by solvothermal method. The crystal structure of the compound was analyzed by single-crystal X-ray diffraction. It has a P1 space group, with lattice parameters a = 10.7190(4) Å, b = 10.8245(5) Å, c = 10.8403(8) Å, a = 80.291(5)°, Β = 70.0015(5)°, Y = 77.531(4)°, V = 1147.97(12) Å3. The secondary building units of 1 consist of 2 central Zn ions, coordinated by 4 carboxylate groups in a bis-monodentate way, forming a square planar configuration of Zn2(CO2)4, known as paddle-wheel units. The paddle-wheels are connected by cubane-1,4-dicarboxylic acid linkers at the edges, resulting in a two-dimensional coordination polymer with a square lattice (sql) underlying network topology. The axial sites of the zinc atoms are occupied by N-methyl-2-pyrrolidone molecules. In this new crystal structure the two-dimensional polymer planes are interstacked by weak dispersion bonds. The axial N-methyl-2-pyrrolidone solvent molecules determine the distances of planar polymer planes. The thermal properties of this new structure were studied by thermogravimetry/mass spectrometry in inert atmosphere. It was found, that the organic linkers in the framework structure do not decompose below 200 °C. The stochiometry of the activated compound is Zn2[C8H6(COO)2]2(C5H9NO)2, as determined by thermogravimetry in oxidative atmosphere.