Li5V2OF11 crystallizes in the triclinic P1 space group. There are ten inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(11), one F(3), one F(4), one F(5), one F(6), and one F(7) atom. In the second Li site, Li(2) is bonded to one F(20), one F(22), one F(3), one F(4), one F(5), and one F(6) atom to form distorted LiF6 octahedra that share  a cornercorner with one V(4)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, and  an edgeedge with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(10), one F(2), one F(20), and one F(21) atom. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one F(11), one F(16), one F(19), and one F(8) atom. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one F(11), one F(14), one F(16), one F(17), one F(5), and one F(9) atom. In the sixth Li site, Li(6) is bonded to one O(1), one F(14), one F(15), one F(18), one F(8), and one F(9) atom to form distorted LiOF5 octahedra that share  a cornercorner with one Li(10)OF5 octahedra,  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra,  an edgeedge with one V(2)OF5 octahedra, and  an edgeedge with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. In the seventh Li site, Li(7) is bonded in a 6-coordinate geometry to one O(1), one F(10), one F(14), one F(15), one F(7), and one F(9) atom. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one F(12), one F(13), one F(16), one F(17), one F(19), and one F(22) atom. In the ninth Li site, Li(9) is bonded in a 6-coordinate geometry to one F(13), one F(18), one F(19), one F(2), one F(20), and one F(3) atom. In the tenth Li site, Li(10) is bonded to one O(2), one F(1), one F(17), one F(18), one F(2), and one F(21) atom to form distorted LiOF5 octahedra that share  a cornercorner with one Li(6)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-62°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(21), one F(22), one F(5), and one F(7) atom to form VOF5 octahedra that share  a cornercorner with one Li(6)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Li(10)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. In the second V site, V(2) is bonded to one O(1), one F(10), one F(2), one F(4), one F(6), and one F(8) atom to form VOF5 octahedra that share  a cornercorner with one Li(10)OF5 octahedra,  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent Li(2)F6 octahedra, and  an edgeedge with one Li(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. In the third V site, V(3) is bonded to one O(2), one F(11), one F(12), one F(14), one F(17), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(4)OF5 octahedra, corners with two equivalent Li(6)OF5 octahedra, and  an edgeedge with one Li(10)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. In the fourth V site, V(4) is bonded to one O(2), one F(13), one F(15), one F(18), one F(19), and one F(20) atom to form VOF5 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent Li(10)OF5 octahedra, and  an edgeedge with one Li(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(6), one Li(7), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(10), one Li(3), one V(3), and one V(4) atom. There are twenty-two inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(10), one Li(3), and one V(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(10), one Li(3), one Li(9), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Li(9) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(5), and one V(1) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one V(2) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(1), one Li(7), and one V(1) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(4), one Li(6), and one V(2) atom. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(5), one Li(6), one Li(7), and one V(3) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(3), one Li(7), and one V(2) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(4), one Li(5), and one V(3) atom. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to one Li(8) and one V(3) atom. In the thirteenth F site, F(13) is bonded in a 3-coordinate geometry to one Li(8), one Li(9), and one V(4) atom. In the fourteenth F site, F(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one Li(6), one Li(7), and one V(3) atom. In the fifteenth F site, F(15) is bonded in a T-shaped geometry to one Li(6), one Li(7), and one V(4) atom. In the sixteenth F site, F(16) is bonded in a trigonal non-coplanar geometry to one Li(4), one Li(5), and one Li(8) atom. In the seventeenth F site, F(17) is bonded in a 4-coordinate geometry to one Li(10), one Li(5), one Li(8), and one V(3) atom. In the eighteenth F site, F(18) is bonded in a 4-coordinate geometry to one Li(10), one Li(6), one Li(9), and one V(4) atom. In the nineteenth F site, F(19) is bonded in a 4-coordinate geometry to one Li(4), one Li(8), one Li(9), and one V(4) atom. In the twentieth F site, F(20) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), one Li(9), and one V(4) atom. In the twenty-first F site, F(21) is bonded in a trigonal planar geometry to one Li(10), one Li(3), and one V(1) atom. In the twenty-second F site, F(22) is bonded in a trigonal non-coplanar geometry to one Li(2), one Li(8), and one V(1) atom.
Li5V2OF11 crystallizes in the triclinic P1 space group. There are ten inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(11), one F(3), one F(4), one F(5), one F(6), and one F(7) atom. The Li(1)-F(11) bond length is 2.46 Å. The Li(1)-F(3) bond length is 1.81 Å. The Li(1)-F(4) bond length is 1.99 Å. The Li(1)-F(5) bond length is 2.52 Å. The Li(1)-F(6) bond length is 2.48 Å. The Li(1)-F(7) bond length is 1.92 Å. In the second Li site, Li(2) is bonded to one F(20), one F(22), one F(3), one F(4), one F(5), and one F(6) atom to form distorted LiF6 octahedra that share  a cornercorner with one V(4)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra, and  an edgeedge with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. The Li(2)-F(20) bond length is 2.03 Å. The Li(2)-F(22) bond length is 2.08 Å. The Li(2)-F(3) bond length is 1.88 Å. The Li(2)-F(4) bond length is 2.05 Å. The Li(2)-F(5) bond length is 2.40 Å. The Li(2)-F(6) bond length is 2.38 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(10), one F(2), one F(20), and one F(21) atom. The Li(3)-O(2) bond length is 2.31 Å. The Li(3)-F(1) bond length is 1.97 Å. The Li(3)-F(10) bond length is 1.95 Å. The Li(3)-F(2) bond length is 2.38 Å. The Li(3)-F(20) bond length is 2.03 Å. The Li(3)-F(21) bond length is 1.93 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one F(11), one F(16), one F(19), and one F(8) atom. The Li(4)-F(11) bond length is 2.05 Å. The Li(4)-F(16) bond length is 1.83 Å. The Li(4)-F(19) bond length is 2.48 Å. The Li(4)-F(8) bond length is 1.92 Å. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one F(11), one F(14), one F(16), one F(17), one F(5), and one F(9) atom. The Li(5)-F(11) bond length is 2.10 Å. The Li(5)-F(14) bond length is 2.20 Å. The Li(5)-F(16) bond length is 1.78 Å. The Li(5)-F(17) bond length is 2.45 Å. The Li(5)-F(5) bond length is 1.99 Å. The Li(5)-F(9) bond length is 2.49 Å. In the sixth Li site, Li(6) is bonded to one O(1), one F(14), one F(15), one F(18), one F(8), and one F(9) atom to form distorted LiOF5 octahedra that share  a cornercorner with one Li(10)OF5 octahedra,  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent V(3)OF5 octahedra,  an edgeedge with one V(2)OF5 octahedra, and  an edgeedge with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The Li(6)-O(1) bond length is 2.38 Å. The Li(6)-F(14) bond length is 2.08 Å. The Li(6)-F(15) bond length is 2.13 Å. The Li(6)-F(18) bond length is 2.00 Å. The Li(6)-F(8) bond length is 1.96 Å. The Li(6)-F(9) bond length is 2.02 Å. In the seventh Li site, Li(7) is bonded in a 6-coordinate geometry to one O(1), one F(10), one F(14), one F(15), one F(7), and one F(9) atom. The Li(7)-O(1) bond length is 2.34 Å. The Li(7)-F(10) bond length is 1.95 Å. The Li(7)-F(14) bond length is 2.44 Å. The Li(7)-F(15) bond length is 1.99 Å. The Li(7)-F(7) bond length is 2.04 Å. The Li(7)-F(9) bond length is 2.01 Å. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one F(12), one F(13), one F(16), one F(17), one F(19), and one F(22) atom. The Li(8)-F(12) bond length is 2.49 Å. The Li(8)-F(13) bond length is 2.36 Å. The Li(8)-F(16) bond length is 1.90 Å. The Li(8)-F(17) bond length is 2.03 Å. The Li(8)-F(19) bond length is 2.12 Å. The Li(8)-F(22) bond length is 2.08 Å. In the ninth Li site, Li(9) is bonded in a 6-coordinate geometry to one F(13), one F(18), one F(19), one F(2), one F(20), and one F(3) atom. The Li(9)-F(13) bond length is 1.99 Å. The Li(9)-F(18) bond length is 2.42 Å. The Li(9)-F(19) bond length is 2.12 Å. The Li(9)-F(2) bond length is 2.12 Å. The Li(9)-F(20) bond length is 2.52 Å. The Li(9)-F(3) bond length is 1.78 Å. In the tenth Li site, Li(10) is bonded to one O(2), one F(1), one F(17), one F(18), one F(2), and one F(21) atom to form distorted LiOF5 octahedra that share  a cornercorner with one Li(6)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(4)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-62°. The Li(10)-O(2) bond length is 2.37 Å. The Li(10)-F(1) bond length is 2.10 Å. The Li(10)-F(17) bond length is 1.98 Å. The Li(10)-F(18) bond length is 1.96 Å. The Li(10)-F(2) bond length is 2.04 Å. The Li(10)-F(21) bond length is 1.96 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(21), one F(22), one F(5), and one F(7) atom to form VOF5 octahedra that share  a cornercorner with one Li(6)OF5 octahedra,  a cornercorner with one V(2)OF5 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Li(10)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The V(1)-O(1) bond length is 1.87 Å. The V(1)-F(1) bond length is 1.90 Å. The V(1)-F(21) bond length is 1.91 Å. The V(1)-F(22) bond length is 1.95 Å. The V(1)-F(5) bond length is 1.87 Å. The V(1)-F(7) bond length is 1.92 Å. In the second V site, V(2) is bonded to one O(1), one F(10), one F(2), one F(4), one F(6), and one F(8) atom to form VOF5 octahedra that share  a cornercorner with one Li(10)OF5 octahedra,  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent Li(2)F6 octahedra, and  an edgeedge with one Li(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. The V(2)-O(1) bond length is 1.87 Å. The V(2)-F(10) bond length is 1.92 Å. The V(2)-F(2) bond length is 1.94 Å. The V(2)-F(4) bond length is 1.98 Å. The V(2)-F(6) bond length is 1.81 Å. The V(2)-F(8) bond length is 1.93 Å. In the third V site, V(3) is bonded to one O(2), one F(11), one F(12), one F(14), one F(17), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(4)OF5 octahedra, corners with two equivalent Li(6)OF5 octahedra, and  an edgeedge with one Li(10)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. The V(3)-O(2) bond length is 1.88 Å. The V(3)-F(11) bond length is 1.97 Å. The V(3)-F(12) bond length is 1.79 Å. The V(3)-F(14) bond length is 1.92 Å. The V(3)-F(17) bond length is 1.93 Å. The V(3)-F(9) bond length is 1.94 Å. In the fourth V site, V(4) is bonded to one O(2), one F(13), one F(15), one F(18), one F(19), and one F(20) atom to form VOF5 octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent Li(10)OF5 octahedra, and  an edgeedge with one Li(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The V(4)-O(2) bond length is 1.83 Å. The V(4)-F(13) bond length is 1.88 Å. The V(4)-F(15) bond length is 1.90 Å. The V(4)-F(18) bond length is 1.95 Å. The V(4)-F(19) bond length is 1.95 Å. The V(4)-F(20) bond length is 1.92 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(6), one Li(7), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(10), one Li(3), one V(3), and one V(4) atom. There are twenty-two inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(10), one Li(3), and one V(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(10), one Li(3), one Li(9), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Li(9) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(5), and one V(1) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one V(2) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(1), one Li(7), and one V(1) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(4), one Li(6), and one V(2) atom. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(5), one Li(6), one Li(7), and one V(3) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(3), one Li(7), and one V(2) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(4), one Li(5), and one V(3) atom. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to one Li(8) and one V(3) atom. In the thirteenth F site, F(13) is bonded in a 3-coordinate geometry to one Li(8), one Li(9), and one V(4) atom. In the fourteenth F site, F(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one Li(6), one Li(7), and one V(3) atom. In the fifteenth F site, F(15) is bonded in a T-shaped geometry to one Li(6), one Li(7), and one V(4) atom. In the sixteenth F site, F(16) is bonded in a trigonal non-coplanar geometry to one Li(4), one Li(5), and one Li(8) atom. In the seventeenth F site, F(17) is bonded in a 4-coordinate geometry to one Li(10), one Li(5), one Li(8), and one V(3) atom. In the eighteenth F site, F(18) is bonded in a 4-coordinate geometry to one Li(10), one Li(6), one Li(9), and one V(4) atom. In the nineteenth F site, F(19) is bonded in a 4-coordinate geometry to one Li(4), one Li(8), one Li(9), and one V(4) atom. In the twentieth F site, F(20) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), one Li(9), and one V(4) atom. In the twenty-first F site, F(21) is bonded in a trigonal planar geometry to one Li(10), one Li(3), and one V(1) atom. In the twenty-second F site, F(22) is bonded in a trigonal non-coplanar geometry to one Li(2), one Li(8), and one V(1) atom.