A rare and novel Cr-substituted polyoxoniobate (PONb), [CrNbO(OH)(HO)], has been synthesized by a combination of hydrothermal and conventional solution methods. The PONb shows an unknown tetrameric structure, which is the largest Cr-containing PONb to date. Interestingly, every two PONb tetramers can be joined together by alkali-metal cations to form a discrete cubelike ionic cluster. The obtained PONb not only enriches the very limited members of the Cr-substituted PONb family but also exhibits high ionic conductivity.
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