Chemistry

Halide-bi-bridged polymers of amide substituted pyridines and -pyrazines: polymorphism, structures, thermal stability and magnetism

Neil Hearne, University of Pretoria
Mark M. Turnbull, Clark University
Christopher P. Landee, Clark University
Elizabet M. Van der Merwe, University of Pretoria
Melanie Rademeyer, University of Pretoria

Abstract

The crystal structures and magnetic properties of seven novel halide-bi-bridged polymers of Cu(ii) and the related organic ligands isonicotinamide, nicotinamide and pyrazinamide were determined. Two concomitant, room temperature polymorphs were identified for each of the compounds di-μ2-chlorido-bis(isonicotinamide) copper(ii) and di-μ2-bromido-bis(isonicotinamide) copper(ii). One of the polymorphs of di-μ2-chlorido-bis(isonicotinamide) copper(ii) displays a non-symmetric halide-bi-bridged portion that has never been reported before, the geometry of which significantly affects the magnetic exchange observed in this compound. In addition, the structures of di-μ2-chlorido-bis(nicotinamide) copper(ii), di-μ2-chlorido-bis(pyrazinamide) copper(ii) and di-μ2-bromido-bis(pyrazinamide) copper(ii) are reported. The effect of the change in organic ligand on the resulting hydrogen bonding interactions, and packing of the polymers, as well as the magnetic isolation of the halide-bi-bridged chains is highlighted. Structures and magnetic properties are compared within the family of compounds, and with related compounds reported in the literature, and magneto-structural correlations are identified, while the thermal stability of the compounds is studied via thermogravimetric analysis.