Four new Mo(V) phosphate structures built up of isotypic Mo12MP8X62 clusters

Four new Mo(V) phosphates with different original structures built up of Mo12MP8X62 (X = O, OH) clusters have been synthesized. Two of them are obtained with a tetramethylammonium cation as the organic template and for M = Cd: [Mo12CdP8X62]Cd-3[N(CH3)(4)](4). 10H(2)O which exhibits a chainlike structure and [Mo12CdP8X62]Cd[N(CH3)(4)](2)(H3O)(6). 5H(2)O with a 3D intersecting tunnel structure. The two other phases contain octyldiammonium cations as templates and are both unidimensional with the formula [Mo12CdP8X62]Cd-2[NH3 (CH2)(8)NH3](3). 7.3H(2)O and [Mo12ZnP8X62]Zn-2[NH3(CH2)(8) NH3](H3O)(4). 8H(2)O. The distribution of hydrogen in the Mo12MP8X62 clusters is established from electrostatic bond valence calculations, for these new structures and for those previously studied, leading to a classification based on the nature and number of the PO4, PO3OH, and PO2(OH)(2) tetrahedra of the clusters. (C) 1999 Academic Press.