Abstract
A new mixed-valent molybdenum monophosphate Li3Mo3O5(PO4)3with an original structure has been isolated. It crystallizes in the space groupP1witha=11.964,b=12.716,c=8.274 Å,α=90.26°,β=96.87°, andγ=89.67°. It is to date the only mixed-valent molybdenum phosphate that exhibits layers of corner-sharing octahedra. The latter, with formulation [Mo8O37]∞, are built up of HTB (hexagonal tungsten bronze) rows of octahedra running along b. The 3D [Mo3P3O17]∞framework results from the stacking of [Mo8O37]∞layers with [MoPO7]∞layers along a, with two successive layers being connected through single PO4tetrahedra. Within this framework, the lithium cations exhibit two kinds of coordination, tetrahedral and pyramidal. Examination of the Mo–O distances and the bond valence calculations suggests an ordering of the Mo(V) and Mo(VI) species, but the magnetic susceptibility measurements show a partial electronic delocalization forT>10 K, whereas an antiferromagnetic ordering is evidenced below 7 K.
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