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]Cd3[N(CH3)4]4.10H2O which exhibits a chain-like structure and [Mo12CdP8X62]Cd[N(CH3)4]2(H3O)6.5H2O with a 3D intersecting tunnel structure. The two other phases contain octyldiammonium cations as templates and are both unidimensional with the formula [Mo12CdP8X62]Cd2[NH3 (CH2)8NH3]3.7.3H2O and [Mo12ZnP8X62]Zn2[NH3(CH2)8 NH3] (H3O)4.8H2O. 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.