A series of Mixed‐Valent Molybdenum Monophosphates, isotypic with leucophosphite represented by CsMo2P2O10 and K1.5Mo2P2O10 · H2O

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Abstract
The structure of two mixed valent molybdenum phosphates, CsMo2P2O10 and K1.5Mo2P2O10 · H2O has been solved from single crystals by X‐ray diffraction in the space group P21/c with a = 9.428(1), b = 9.943(2), c = 12.348(2) Å and β = 127.38(1)° for CsMo2P2O10 and a = 9.721(2), b = 9.805(3), c = 12.329(3) Å and β = 128.73(2)° for K1.5Mo2P2O10 · H2O. These compounds isotypic with NH4Mo2P2O10 · H2O and RbMo2P2O10 · (1 − x)H2O exhibit the leucophosphite structure. The possibility of cationic non stoichiometry in this structure is also shown by the synthesis of two isotypic compounds A1.5Mo2P2O10 · xH2O (A = Rb, Tl). In these monophosphates, one site Mo(1) is fully occupied by MoV, whereas the other octahedral site Mo(2) exhibits a variable valency MoIIIMoIV to MoV. The main difference between these different phosphates deals with the distribution of the A cations inside the tunnels, depending upon their size and their content.