V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. In the second V site, V(2) is bonded to one O(1), three equivalent O(2), and two equivalent F(1) atoms to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. F(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms.
V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. All V(1)-O(1) bond lengths are 1.99 Å. Both V(1)-F(1) bond lengths are 2.03 Å. In the second V site, V(2) is bonded to one O(1), three equivalent O(2), and two equivalent F(1) atoms to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The V(2)-O(1) bond length is 1.90 Å. There are a spread of V(2)-O(2) bond distances ranging from 1.84-1.98 Å. There is one shorter (2.06 Å) and one longer (2.10 Å) V(2)-F(1) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. F(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms.