A new porous 2D coordination polymer built by copper(II) and trimesic acid

Abstract

A 2D porous material, Cu3(tmen)3(tma)2(H2O)2 · 6.5H2O [tmen = N,N,N′,N′-tetramethylethane-1,2-diamine; tmaH3 = 1,3,5-benzenetricarboxylic acid/trimesic acid], has been synthesized and characterized by X-ray single crystal analysis, variable temperature magnetic measurements, IR spectra and XRPD pattern. The complex consists of 2D layers built by three crystallographically independent Cu(tmen) moieties bridged by tma anions. Of the three copper ions, Cu(1) and Cu(2) present distorted square pyramidal coordination geometry, while the third exhibits a severely distorted octahedral environment. The Cu(1)(tmen) and Cu(2)(tmen) building blocks bridged by tma anions give rise to chains with a zig-zag motif, which are cross-connected by Cu(3)(tmen)–tma polymers sharing metal ions Cu(2) through pendant tma carboxylates. The resulting 2D architecture extends in the crystallographic ab-plane. The adjacent sheets are embedded through the Cu(3)(tmen)–tma chains, leaving H2O-filled channels. There are 6.5 lattice water molecules per formula unit, some of which are disordered. Upon heating, the lattice water molecules get eliminated without destroying the crystal morphology and the compound rehydrated reversibly on exposure to humid atmosphere. Magnetic data of the complex have been fitted considering isolated irregular Cu3 triangles (three different J parameters) by applying the clumag program. The best fit indicates three close comparable J parameters and very weak antiferromagnetic interactions are operative between the metal centers.