V3OF7 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(13), one F(4), one F(7), and two equivalent F(11) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(5)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, and edges with two equivalent V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-31°. In the second V site, V(2) is bonded to one O(2), one F(12), one F(6), one F(9), and two equivalent F(14) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(6)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, and edges with two equivalent V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-31°. In the third V site, V(3) is bonded to one F(5), one F(6), one F(7), one F(8), and two equivalent F(1) atoms to form VF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(5)OF5 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with two equivalent V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-30°. In the fourth V site, V(4) is bonded to one F(10), one F(3), one F(4), one F(9), and two equivalent F(2) atoms to form VF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(5)OF5 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with two equivalent V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-30°. In the fifth V site, V(5) is bonded to one O(1), one F(14), one F(3), one F(8), and two equivalent F(12) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-31°. In the sixth V site, V(6) is bonded to one O(2), one F(10), one F(11), one F(5), and two equivalent F(13) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra, and edges with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-31°. 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 V(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(3) atoms. In the second F site, F(2) is bonded in a linear geometry to two equivalent V(4) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(4) and one V(5) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) 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 bent 150 degrees geometry to one V(3) and one V(5) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(4) and one V(6) atom. In the eleventh F site, F(11) is bonded in a distorted T-shaped geometry to one V(6) and two equivalent V(1) atoms. In the twelfth F site, F(12) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(5) atoms. In the thirteenth F site, F(13) is bonded in a distorted T-shaped geometry to one V(1) and two equivalent V(6) atoms. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(2) atoms.
V3OF7 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(13), one F(4), one F(7), and two equivalent F(11) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(5)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, and edges with two equivalent V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-31°. The V(1)-O(1) bond length is 1.84 Å. The V(1)-F(13) bond length is 2.16 Å. The V(1)-F(4) bond length is 1.97 Å. The V(1)-F(7) bond length is 2.00 Å. There is one shorter (2.07 Å) and one longer (2.08 Å) V(1)-F(11) bond length. In the second V site, V(2) is bonded to one O(2), one F(12), one F(6), one F(9), and two equivalent F(14) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(6)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, and edges with two equivalent V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-31°. The V(2)-O(2) bond length is 1.84 Å. The V(2)-F(12) bond length is 2.17 Å. The V(2)-F(6) bond length is 1.97 Å. The V(2)-F(9) bond length is 2.01 Å. Both V(2)-F(14) bond lengths are 2.08 Å. In the third V site, V(3) is bonded to one F(5), one F(6), one F(7), one F(8), and two equivalent F(1) atoms to form VF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(5)OF5 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with two equivalent V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-30°. The V(3)-F(5) bond length is 1.96 Å. The V(3)-F(6) bond length is 1.98 Å. The V(3)-F(7) bond length is 1.97 Å. The V(3)-F(8) bond length is 1.94 Å. There is one shorter (2.01 Å) and one longer (2.02 Å) V(3)-F(1) bond length. In the fourth V site, V(4) is bonded to one F(10), one F(3), one F(4), one F(9), and two equivalent F(2) atoms to form VF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(5)OF5 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with two equivalent V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 2-30°. The V(4)-F(10) bond length is 1.96 Å. The V(4)-F(3) bond length is 1.97 Å. The V(4)-F(4) bond length is 1.98 Å. The V(4)-F(9) bond length is 1.96 Å. There is one shorter (2.00 Å) and one longer (2.02 Å) V(4)-F(2) bond length. In the fifth V site, V(5) is bonded to one O(1), one F(14), one F(3), one F(8), and two equivalent F(12) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent V(5)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-31°. The V(5)-O(1) bond length is 1.84 Å. The V(5)-F(14) bond length is 2.16 Å. The V(5)-F(3) bond length is 1.98 Å. The V(5)-F(8) bond length is 2.02 Å. There is one shorter (2.07 Å) and one longer (2.08 Å) V(5)-F(12) bond length. In the sixth V site, V(6) is bonded to one O(2), one F(10), one F(11), one F(5), and two equivalent F(13) atoms to form VOF5 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(6)OF5 octahedra, and edges with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-31°. The V(6)-O(2) bond length is 1.84 Å. The V(6)-F(10) bond length is 2.01 Å. The V(6)-F(11) bond length is 2.15 Å. The V(6)-F(5) bond length is 1.98 Å. There is one shorter (2.07 Å) and one longer (2.08 Å) V(6)-F(13) bond length. 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 V(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(3) atoms. In the second F site, F(2) is bonded in a linear geometry to two equivalent V(4) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(4) and one V(5) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) 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 bent 150 degrees geometry to one V(3) and one V(5) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(4) and one V(6) atom. In the eleventh F site, F(11) is bonded in a distorted T-shaped geometry to one V(6) and two equivalent V(1) atoms. In the twelfth F site, F(12) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(5) atoms. In the thirteenth F site, F(13) is bonded in a distorted T-shaped geometry to one V(1) and two equivalent V(6) atoms. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(2) atoms.