Five manganese(II) complexes with seven- or eight-coordinated Mn(II), revealing different coordination modes for the nitrato ligands

Four seven-coordinated manganese(II) complexes [Mn(tpa)(eta(1)-NO3)(eta(2)-NO3)] (1), [Mn(bpia)(eta(1)-NO3)(eta(2)-NO3)] (2), [Mn(tpa)(eta(1)-NO3)(eta(2)-NO3)] (3), [Mn(tpa)(eta(1)-NO3)(eta(2)-NO3)] (4), and one octacoordinated manganese(II) complex [Mn(bppza)(mu(2)-NO3)(2)] (5) have been synthesized and characterized using the tripodal tetradentate ligands tpa, bpia, bipa, ipqa, and bppza (tpa: tris(2-pyridylmethyl)amine, bpia: bis(2-pyridylmethyl)(2-(N-methyl)imidazolylmethyl)amine, bipa: bis-(2-(N-methyl)imidazolylmethyl)(2-pyridylmethyl)amine, ipqa: (2-(N-methyl)imidazolylmethyl)(2-pyridylmethyl)(2-quinolylmethyl)amine, and bppza: bis(2-pyridylmethyl)(2-pyrazylmethyl)amine). The crystal structures for all compounds have been determined. 1, 2 and 3 crystallize in the triclinic space group P (1) over bar, 4 crystallizes in the orthorhombic space group Pbca, whereas the eight-coordinated 5 crystallizes in the monoclinic space group P2(1)/n. All compounds have one bidentate bound nitrate group in common. The coordination number and its geometry depend on the coordination mode of the second nitrate group. The coordination polyhedron for 1, 2, 3 and 4 is best described as an oblate octahedron and the one for 5 as a doubly oblate octahedron. (C) 2004 Elsevier B.V. All rights reserved.