Structural and magnetic properties of carboxylato-bridged manganese(II) complexes involving tetradentate ligands: discrete complex and 1D polymers. Dependence of J on the nature of the carboxylato bridge.

The crystal structure of an inorganic linear polymer consisting of Mn(II) and an N-centered tripodal ligand N,N-bis(2-(6-methyl)pyridylmethyl)glycinate is presented (1, C(16)H(20)N(3)O(3)F(6)P(1)Mn(1), a = 9.993(2) A, b = 13.285(3) A, c = 16.040(3) A, orthorhombic, Pnam, Z = 4). The polymeric structure is ensured by carboxylato ligands connecting two Mn(II) in a rather rare syn-anti geometry. The magnetic properties of this infinite chain have been investigated, together with the magnetic properties of a dimeric Mn(II) compound (3) from a closely related ligand [N,N-bis[(1-methylimidazol-2-yl)-methyl)glycinate] involving an unusual bis(monatomic-carboxylato) bridge. The inorganic polymer 1 shows a pseudo-2D magnetic structure, with a major interaction pathway along the chain (J/k = -0.172 +/- 0.005 K) and an interchain minor one (zJ'/k = -0.006 +/- 0.004 K). These properties are reminiscent of those from a closely related previously reported inorganic Mn(II) polymer (2 obtained from manganese(II) and N,N-(2-pyridylmethyl)((1-methylimidazol-2-yl)methyl)glycinate). The dimer 3 shows a small antiferromagnetic coupling of J/k = -0.693 +/- 0.016 K. To address the influence of the carboxylato bridging mode on the magnetic properties, these complexes are compared to a series of compounds involving carboxylato bridges of several geometries between Mn(II) ions. Carboxylato bridges induce usually antiferromagnetic coupling, with the magnitude of the interaction (/J/) increasing with the number of bridges. The J value is dependent on the bridging mode. The syn-syn bridge is an efficient pathway, even by comparison with the monatomic [(mu-eta(1)-carboxylato)] bridge.