VPO4F crystallizes in the monoclinic C2/c space group. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 37-40°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.
VPO4F crystallizes in the monoclinic C2/c space group. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. Both V(1)-O(1) bond lengths are 1.96 Å. Both V(1)-O(2) bond lengths are 1.87 Å. Both V(1)-F(1) bond lengths are 1.98 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 37-40°. Both P(1)-O(1) bond lengths are 1.54 Å. Both P(1)-O(2) bond lengths are 1.56 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.