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A Cubane-Substituted Polyoxoanion: Structure and Magnetic Properties of Cs(2)[H(2)PW(9)Ni(4)O(34)(OH)(3)(H(2)O)(6)].5H(2)O. 1999

Ulrich Kortz, and André Tézé, and Gilbert Hervé
Institut de Réactivité, Électrochimie et Microporosités, UMR C0173, Université de Versailles, 45 Avenue des États Unis, 78035 Versailles Cedex, France.

The novel polyoxometalate [H(2)PW(9)Ni(4)O(34)(OH)(3)(H(2)O)(6)](2)(-) (1) has been synthesized and characterized by IR spectroscopy, polarography, elemental analysis, and magnetic measurements. An X-ray single-crystal analysis was carried out on Cs(2)[H(2)PW(9)Ni(4)O(34)(OH)(3)(H(2)O)(6)].5H(2)O, which crystallizes in the orthorhombic system, space group Pbcn, with a = 24.3131(3) Å, b = 21.5400(1) Å, c = 19.8936(3) Å, V = 10418.4(2) Å(3), Z = 8, and rho(calcd) = 3.767 g/cm(3). Structural analysis based on 14 734 independent reflections leads to a solution, R = 8.04% (I > 2sigma(I)). Anion 1 consists of a Ni(4)O(4) cubane fragment which is inserted into a trivacant lacunary B-alpha-[PW(9)O(34)](9)(-) Keggin unit. Magnetic measurements show that the Ni-Ni exchange interactions are ferromagnetic.

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