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The structure of the title compound, sodium lithium decavanadate eicosahydrate, Na5.22Li0.78[V10O28]·20H2O, is characterised by [V10O28]6- polyanions which are linked by hydrogen bonds and Na+ ions. The centrosymmetric [V10O28]6- polyanion consists of ten distorted VO6 edge-sharing octahedra.
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