V3OF7 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 3-32°. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), and three equivalent F(4) atoms to form distorted VOF5 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-32°. O(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms.
V3OF7 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 3-32°. Both V(1)-F(1) bond lengths are 2.01 Å. Both V(1)-F(2) bond lengths are 1.96 Å. Both V(1)-F(3) bond lengths are 1.97 Å. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), and three equivalent F(4) atoms to form distorted VOF5 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-32°. The V(2)-O(1) bond length is 1.81 Å. The V(2)-F(2) bond length is 1.99 Å. The V(2)-F(3) bond length is 2.01 Å. There are two shorter (2.07 Å) and one longer (2.17 Å) V(2)-F(4) bond length. O(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms.