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DOI: 10.1039/A809671F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 1805-1812

Chains, planes, and tunnels of metal diphosphonates: synthesis, structure, and characterization of Na3Co(O3PCH2PO3)(OH), Na3Mg(O3PCH2PO3)F·H2O, Na2Co(O3PCH2PO3)·H2O, NaCo2(O3PCH2CH2CH2PO3)(OH), and Co2(O3PCH2PO3)(H2O)

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Anne Distler, Douglas L. Lohse and Slavi C. Sevov

Abstract

Four cobalt(II) and one magnesium diphosphonates with one-, two-, and three-dimensional structures have been synthesized and characterized structurally, thermally, magnetically, and spectroscopically (IR and UV-VIS). Isolated chains of corner-sharing octahedra (trans OH or F groups) are observed in the colorless Na3Co(O3PCH2PO3)(µ-OH) 1 and in the nearly isostructural Na3Mg(O3PCH2PO3)(µ-F)·H2O 2. Planes characterize the structures of the layered Na2Co(O3PCH2PO3)·H2O 3 with square-pyramidal cobalt, and of NaCo2(O3PCH2CH2CH2PO3)(µ3-OH) 4 with octahedral and trigonal-bipyramidal cobalt. Hydrophobic tunnels are found in Co2(O3PCH2PO3)(H2O) 5. The diphosphonates co-ordinate as tetradentate ligands in 1 and 2, pentadentate ligands in 3, and hexadentate ligands in 4 and 5. Four of the six Co–O distances of the CoO6 octahedra in 1 are anomalously long. Remarkably, the compound is colorless, a quite unusual phenomenon for a cobalt(II) compound. Magnetic measurements showed Curie–Weiss behavior for 1, 3, 4, and 5, but also some unusual transitions at low temperatures for compound 1.

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