V2F7 crystallizes in the monoclinic P2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one F(13), one F(2), one F(6), one F(8), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 33-42°. In the second V site, V(2) is bonded to one F(10), one F(11), one F(4), one F(7), and two equivalent F(1) atoms to form a mixture of distorted corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-51°. In the third V site, V(3) is bonded to one F(12), one F(13), one F(14), one F(5), one F(8), and one F(9) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. In the fourth V site, V(4) is bonded to one F(10), one F(14), one F(7), one F(9), and two equivalent F(11) atoms to form a mixture of corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-51°. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the second F site, F(2) is bonded in a single-bond geometry to one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a single-bond geometry to one V(2) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(3) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(1) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one V(2) and one V(4) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(4) atoms. In the twelfth F site, F(12) is bonded in a single-bond geometry to one V(3) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom.
V2F7 crystallizes in the monoclinic P2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one F(13), one F(2), one F(6), one F(8), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 33-42°. The V(1)-F(13) bond length is 1.97 Å. The V(1)-F(2) bond length is 1.75 Å. The V(1)-F(6) bond length is 1.77 Å. The V(1)-F(8) bond length is 2.01 Å. There is one shorter (1.92 Å) and one longer (2.02 Å) V(1)-F(3) bond length. In the second V site, V(2) is bonded to one F(10), one F(11), one F(4), one F(7), and two equivalent F(1) atoms to form a mixture of distorted corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-51°. The V(2)-F(10) bond length is 2.10 Å. The V(2)-F(11) bond length is 2.35 Å. The V(2)-F(4) bond length is 1.80 Å. The V(2)-F(7) bond length is 2.04 Å. There is one shorter (1.96 Å) and one longer (2.02 Å) V(2)-F(1) bond length. In the third V site, V(3) is bonded to one F(12), one F(13), one F(14), one F(5), one F(8), and one F(9) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. The V(3)-F(12) bond length is 1.77 Å. The V(3)-F(13) bond length is 2.00 Å. The V(3)-F(14) bond length is 1.98 Å. The V(3)-F(5) bond length is 1.76 Å. The V(3)-F(8) bond length is 1.95 Å. The V(3)-F(9) bond length is 1.97 Å. In the fourth V site, V(4) is bonded to one F(10), one F(14), one F(7), one F(9), and two equivalent F(11) atoms to form a mixture of corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-51°. The V(4)-F(10) bond length is 1.93 Å. The V(4)-F(14) bond length is 1.98 Å. The V(4)-F(7) bond length is 1.95 Å. The V(4)-F(9) bond length is 1.95 Å. Both V(4)-F(11) bond lengths are 2.07 Å. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the second F site, F(2) is bonded in a single-bond geometry to one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a single-bond geometry to one V(2) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(3) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(1) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one V(2) and one V(4) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(4) atoms. In the twelfth F site, F(12) is bonded in a single-bond geometry to one V(3) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom.