Inorganic Chemistry, Vol.50, No.15, 7284-7294, 2011
Synthesis, Structures, and Magnetism of Copper(II) and Manganese(II) Coordination Polymers with Azide and Pyridylbenzoates
Three transition-metal coordination polymers with azide and/or carboxylate bridges have been synthesized from 4-(3-pyridyl)benzoic acid (4,3-Hpybz) and 4-(4-pyridyl)benzoic acid (4,4-Hpybz) and characterized by X-ray crystallography and magnetic measurements. Compound 1, [Cu(4,3-pybz)(N-3)](rv) consists of 2D coordination networks in which the uniform chains with (mu-EO-N-3)(mu-COO) double bridges are cross-linked by the 4,3-pybz ligands. Compound 2, [Cu-2(4,4-pybz)(3)(N-3)]n center dot 3nH(2)O, consists of 2-fold interpenetrated 3D coordination networks with the alpha-Po topology, in which the six-connected dinuclear motifs with mixed (mu-EO-N-3)(mu-COO)(2) (EO = end-on) triple bridges are linked by the 4,4-pybz spacers. Compound 3, [Mn(4,4-pybz)(N-3)(H2O)(2)](n), contains 2D manganese(II) coordination networks in which the chains with single mu-EE-N-3 bridges (EE = end-to-end) are interlinked by the 4,4-pybz ligands, and the structure also features a 2D hydrogen-bonded network in which Mn-II ions are linked by double triatomic bridges, (mu-EE-N-3) (O-H center dot center dot center dot N) and (O-H center dot center dot center dot O)(2). Magnetic studies indicated that the mixed azide and carboxylate bridges in 1 and 2 induce ferromagnetic coupling between Cu-II ions and that 3 features antiferromagnetic coupling through the EE-azide bridge. In addition, compound 1 exhibits antiferromagnetic ordering below 6.2 K and behaves as a field-induced metamagnet. A magnetostructural survey indicates a general trend that the ferromagnetic coupling through the mixed bridges decreases as the Cu-N-Cu angle increases.