Abstract
A new mixed-valent vanadium tungsten monophosphate Cs5V2W4O13(PO4)4has been synthesized in air in spite of the presence of V(IV). It crystallizes in the space groupCmc21witha=14.948(1),b=20.008(2), andc=9.942(1) Å. Its original structure, built up from W2O11bioctahedra, P2VO10tritetrahedra units, and VO5pyramids, can be described from [W2P2O13]∞layers parallel to (100) interconnected through VO4tetrahedra and VO5pyramids. This open framework forms intersecting tunnels running along a→ and c→, where the Cs+cations are located. Bond strength–bond length calculations and magnetic measurements show that the electrons are localized, V(IV) sitting in the VO5pyramid, whereas the VO4tetrahedra and WO6octahedra are occupied by V(V) and W(VI), respectively.
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