Nb2O2F3: A Reduced Niobium (III/IV) Oxyfluoride with a Complex Structural, Magnetic, and Electronic Phase Transition

A new niobium oxyfluoride, Nb2O2F3, synthesized through the reaction of Nb, SnO, and SnF2 in Sn flux, within welded Nb containers, crystallizes in a monoclinic structure (space group: I2/a; a = 5.7048(1)­Å, b = 5.1610(1)­Å, c = 12.2285(2)­Å, β = 95.751(1)°). It features [Nb2X10] units (X = O, F), with short (2.5739(1) Å) Nb–Nb bonds, that are linked through shared O/F vertices to form a 3D structure configurationally isotypic to ζ-Nb2O5. Nb2O2F3 undergoes a structural transition at ∼90 K to a triclinic structure (space group: P1̅; a = 5.1791(5)­Å, b = 5.7043(6)­Å, c = 6.8911(7)­Å, α = 108.669(3)°, β = 109.922(2)°, γ = 90.332(3)°). The transition is described as a disproportionation or charge ordering of [Nb2]7+ dimers: (2­[Nb2]7+ → [Nb2]6+ + [Nb2]8+), resulting in doubly (2.5000(9) Å) and singly bonded (2.6560(9) Å) Nb2 dimers. The structural transition is accompanied by an unusual field-independent “spin-gap-like” magnetic transition.