Hydrothermal Synthesis and Structures of Two New Molybdenum Phosphate Compounds based on Keggin Cluster Units

Two new molybdenum phosphate complexes, [Cu2(phen)4(μ‐Cl)][PMo12O40]·H2O (phen = 1,10‐phenanthroline) (1) and (Hbpy)[CuI(bpy)]2[PMoV2MoVI10O39] (bpy = 4,4′‐bipyridine) (2), have been prepared under mild hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction. Compounds 1 and 2 crystallize in triclinic system, space group ${\rm P}{\bar 1}$, with a = 12.5458(7) Å, b = 13.4486(8) Å, c = 21.2406(12) Å, α = 99.7020(10)°, β = 94.2320(10)°, γ = 95.0890(10)°, V = 3504.2(3) Å3 and Z = 2 for 1, and a = 10.7871(6) Å, b = 10.9016(6) Å, c = 12.7897(7) Å, α = 96.8500(10)°, β = 110.0850(10)°, γ = 103.5800(10)°, V = 1339.74(13) Å3 and Z = 1 for 2. Compound 1 contains a [Cu2(phen)4(μ‐Cl)]3+ cation in which two similar [Cu(phen)2] units are bridged by one chlorine atom. Compound 2 contains one‐dimensional straight chain of Keggin polyoxoanions [PMoV2MoVI10O39]n3− and two linear cationic chains of [CuI(bpy)]nn+. The molecular packing shows a two‐dimensional network, which is formed by the cross of the linear Keggin anions and Cu‐bpy cations.