LiV2OF5 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one F(15), one F(5), one F(7), and one F(8) atom. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one O(2), one F(14), and one F(15) atom. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(1), one F(1), one F(11), one F(14), and one F(2) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(10), one F(13), one F(15), one F(5), one F(6), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, and corners with four equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-43°. In the second V site, V(2) is bonded to one O(1), one F(1), one F(3), one F(5), one F(7), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(3)O2F4 octahedra, and corners with four equivalent V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 33-41°. In the third V site, V(3) is bonded to one O(1), one O(2), one F(12), one F(14), one F(2), and one F(4) atom to form VO2F4 octahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(2)OF5 octahedra, and corners with four equivalent V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. In the fourth V site, V(4) is bonded to one O(2), one O(3), one F(10), one F(13), one F(15), and one F(8) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)O2F4 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-43°. In the fifth V site, V(5) is bonded to one F(11), one F(12), one F(14), one F(2), one F(4), and one F(6) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with four equivalent V(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-43°. In the sixth V site, V(6) is bonded to one O(3), one F(1), one F(11), one F(3), one F(7), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(4)O2F4 octahedra, and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 33-41°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one V(6) atom. There are fifteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(6) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(6) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(4) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the eleventh F site, F(11) is bonded in a distorted T-shaped geometry to one Li(3), one V(5), and one V(6) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(3), and one V(5) atom. In the fifteenth F site, F(15) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(4) atom.
LiV2OF5 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one F(15), one F(5), one F(7), and one F(8) atom. The Li(1)-O(3) bond length is 1.92 Å. The Li(1)-F(15) bond length is 2.45 Å. The Li(1)-F(5) bond length is 2.36 Å. The Li(1)-F(7) bond length is 1.94 Å. The Li(1)-F(8) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one O(2), one F(14), and one F(15) atom. The Li(2)-O(2) bond length is 1.91 Å. The Li(2)-F(14) bond length is 1.92 Å. The Li(2)-F(15) bond length is 1.93 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(1), one F(1), one F(11), one F(14), and one F(2) atom. The Li(3)-O(1) bond length is 1.91 Å. The Li(3)-F(1) bond length is 1.92 Å. The Li(3)-F(11) bond length is 2.42 Å. The Li(3)-F(14) bond length is 2.49 Å. The Li(3)-F(2) bond length is 1.97 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(10), one F(13), one F(15), one F(5), one F(6), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, and corners with four equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-43°. The V(1)-F(10) bond length is 1.95 Å. The V(1)-F(13) bond length is 1.94 Å. The V(1)-F(15) bond length is 2.05 Å. The V(1)-F(5) bond length is 1.93 Å. The V(1)-F(6) bond length is 1.99 Å. The V(1)-F(8) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(1), one F(1), one F(3), one F(5), one F(7), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(3)O2F4 octahedra, and corners with four equivalent V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 33-41°. The V(2)-O(1) bond length is 1.86 Å. The V(2)-F(1) bond length is 2.04 Å. The V(2)-F(3) bond length is 2.02 Å. The V(2)-F(5) bond length is 2.11 Å. The V(2)-F(7) bond length is 2.09 Å. The V(2)-F(9) bond length is 1.98 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one F(12), one F(14), one F(2), and one F(4) atom to form VO2F4 octahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(2)OF5 octahedra, and corners with four equivalent V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. The V(3)-O(1) bond length is 1.93 Å. The V(3)-O(2) bond length is 1.91 Å. The V(3)-F(12) bond length is 2.07 Å. The V(3)-F(14) bond length is 2.07 Å. The V(3)-F(2) bond length is 2.08 Å. The V(3)-F(4) bond length is 2.08 Å. In the fourth V site, V(4) is bonded to one O(2), one O(3), one F(10), one F(13), one F(15), and one F(8) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)O2F4 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-43°. The V(4)-O(2) bond length is 1.91 Å. The V(4)-O(3) bond length is 1.93 Å. The V(4)-F(10) bond length is 2.07 Å. The V(4)-F(13) bond length is 2.08 Å. The V(4)-F(15) bond length is 2.08 Å. The V(4)-F(8) bond length is 2.08 Å. In the fifth V site, V(5) is bonded to one F(11), one F(12), one F(14), one F(2), one F(4), and one F(6) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(6)OF5 octahedra, and corners with four equivalent V(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-43°. The V(5)-F(11) bond length is 1.94 Å. The V(5)-F(12) bond length is 1.93 Å. The V(5)-F(14) bond length is 2.06 Å. The V(5)-F(2) bond length is 2.04 Å. The V(5)-F(4) bond length is 1.94 Å. The V(5)-F(6) bond length is 1.99 Å. In the sixth V site, V(6) is bonded to one O(3), one F(1), one F(11), one F(3), one F(7), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(4)O2F4 octahedra, and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 33-41°. The V(6)-O(3) bond length is 1.85 Å. The V(6)-F(1) bond length is 2.10 Å. The V(6)-F(11) bond length is 2.10 Å. The V(6)-F(3) bond length is 1.97 Å. The V(6)-F(7) bond length is 2.05 Å. The V(6)-F(9) bond length is 2.02 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one V(6) atom. There are fifteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(6) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(6) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(4) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the eleventh F site, F(11) is bonded in a distorted T-shaped geometry to one Li(3), one V(5), and one V(6) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(3), and one V(5) atom. In the fifteenth F site, F(15) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(4) atom.