V3OF7 crystallizes in the monoclinic Pm space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(7) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with two equivalent V(2)OF5 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-32°. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), one F(5), and two equivalent F(4) atoms to form distorted VOF5 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra, corners with three equivalent V(2)OF5 octahedra, and edges with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-32°. In the third V site, V(3) is bonded to one O(2), one F(4), one F(6), one F(7), and two equivalent F(5) atoms to form distorted VOF5 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra, corners with three equivalent V(3)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-32°. In the fourth V site, V(4) is bonded to two equivalent F(2), two equivalent F(6), and two equivalent F(8) atoms to form VF6 octahedra that share corners with two equivalent V(4)F6 octahedra, corners with two equivalent V(2)OF5 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-32°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. There are eight 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(2) and one V(4) 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 one V(3) and two equivalent V(2) atoms. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(3) atoms. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(4) atoms.
V3OF7 crystallizes in the monoclinic Pm space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(7) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with two equivalent V(2)OF5 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-32°. There is one shorter (2.00 Å) and one longer (2.01 Å) V(1)-F(1) bond length. Both V(1)-F(3) bond lengths are 1.97 Å. Both V(1)-F(7) 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), one F(5), and two equivalent F(4) atoms to form distorted VOF5 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra, corners with three equivalent V(2)OF5 octahedra, and edges with two equivalent V(3)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. The V(2)-F(5) bond length is 2.18 Å. There is one shorter (2.06 Å) and one longer (2.07 Å) V(2)-F(4) bond length. In the third V site, V(3) is bonded to one O(2), one F(4), one F(6), one F(7), and two equivalent F(5) atoms to form distorted VOF5 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra, corners with three equivalent V(3)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-32°. The V(3)-O(2) bond length is 1.81 Å. The V(3)-F(4) bond length is 2.18 Å. The V(3)-F(6) bond length is 2.01 Å. The V(3)-F(7) bond length is 1.99 Å. There is one shorter (2.06 Å) and one longer (2.07 Å) V(3)-F(5) bond length. In the fourth V site, V(4) is bonded to two equivalent F(2), two equivalent F(6), and two equivalent F(8) atoms to form VF6 octahedra that share corners with two equivalent V(4)F6 octahedra, corners with two equivalent V(2)OF5 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-32°. Both V(4)-F(2) bond lengths are 1.97 Å. Both V(4)-F(6) bond lengths are 1.97 Å. There is one shorter (2.00 Å) and one longer (2.01 Å) V(4)-F(8) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. There are eight 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(2) and one V(4) 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 one V(3) and two equivalent V(2) atoms. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(3) atoms. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(4) atoms.