Li4V3OF11 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(16), one F(5), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(4)OF5 octahedra,  a cornercorner with one V(5)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-68°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(10), one F(19), one F(2), one F(4), and one F(8) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one F(18), one F(3), one F(6), and one F(9) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(14), one F(21), one F(3), and one F(6) atom. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one F(13), one F(16), one F(17), one F(5), and one F(7) atom. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(1), one F(10), one F(13), one F(15), one F(19), and one F(8) atom. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one F(12), one F(15), one F(19), one F(20), and one F(4) atom. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one O(2), one F(11), one F(14), one F(18), one F(21), and one F(3) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(10), one F(13), one F(2), one F(5), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(5)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. In the second V site, V(2) is bonded to one F(12), one F(20), one F(22), one F(4), one F(6), and one F(9) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. In the third V site, V(3) is bonded to one O(2), one F(1), one F(11), one F(14), one F(21), and one F(7) atom to form VOF5 octahedra that share corners with four equivalent V(4)OF5 octahedra and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-47°. In the fourth V site, V(4) is bonded to one O(2), one F(1), one F(11), one F(17), one F(21), and one F(3) atom to form VOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-47°. In the fifth V site, V(5) is bonded to one O(1), one F(10), one F(13), one F(16), one F(19), and one F(2) atom to form VOF5 octahedra that share corners with four equivalent V(1)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. In the sixth V site, V(6) is bonded to one F(12), one F(15), one F(18), one F(20), one F(22), and one F(9) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Li(6), one V(1), and one V(5) atom. In the second O site, O(2) is bonded in a distorted tetrahedral geometry to one Li(4), one Li(8), 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 3-coordinate geometry to one Li(1), one Li(4), one V(3), and one V(4) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(2), one V(1), and one V(5) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), one Li(8), and one V(4) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(2), one Li(7), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(5), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(5), and one V(3) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(2), one Li(6), and one V(1) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one V(6) atom. In the tenth F site, F(10) is bonded to one Li(2), one Li(6), one V(1), and one V(5) atom to form distorted corner-sharing FLi2V2 trigonal pyramids. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one Li(8), one V(3), and one V(4) atom. In the twelfth F site, F(12) is bonded in a trigonal planar geometry to one Li(7), one V(2), and one V(6) atom. In the thirteenth F site, F(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one Li(6), one V(1), and one V(5) atom. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(4), one Li(8), and one V(3) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal non-coplanar geometry to one Li(6), one Li(7), and one V(6) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Li(5), and one V(5) atom. In the seventeenth F site, F(17) is bonded in a bent 120 degrees geometry to one Li(5) and one V(4) atom. In the eighteenth F site, F(18) is bonded in a T-shaped geometry to one Li(3), one Li(8), and one V(6) atom. In the nineteenth F site, F(19) is bonded to one Li(2), one Li(6), one Li(7), and one V(5) atom to form distorted corner-sharing FLi3V trigonal pyramids. In the twentieth F site, F(20) is bonded in a 3-coordinate geometry to one Li(7), one V(2), and one V(6) atom. In the twenty-first F site, F(21) is bonded in a 4-coordinate geometry to one Li(4), one Li(8), one V(3), and one V(4) atom. In the twenty-second F site, F(22) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(6) atom.
Li4V3OF11 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(16), one F(5), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(4)OF5 octahedra,  a cornercorner with one V(5)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-68°. The Li(1)-F(1) bond length is 1.99 Å. The Li(1)-F(16) bond length is 1.90 Å. The Li(1)-F(5) bond length is 1.93 Å. The Li(1)-F(7) bond length is 2.05 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(10), one F(19), one F(2), one F(4), and one F(8) atom. The Li(2)-O(1) bond length is 2.56 Å. The Li(2)-F(10) bond length is 1.95 Å. The Li(2)-F(19) bond length is 2.30 Å. The Li(2)-F(2) bond length is 2.13 Å. The Li(2)-F(4) bond length is 1.99 Å. The Li(2)-F(8) bond length is 1.92 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one F(18), one F(3), one F(6), and one F(9) atom. The Li(3)-F(18) bond length is 2.01 Å. The Li(3)-F(3) bond length is 1.82 Å. The Li(3)-F(6) bond length is 1.91 Å. The Li(3)-F(9) bond length is 2.16 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(14), one F(21), one F(3), and one F(6) atom. The Li(4)-O(2) bond length is 2.37 Å. The Li(4)-F(1) bond length is 2.51 Å. The Li(4)-F(14) bond length is 1.98 Å. The Li(4)-F(21) bond length is 2.08 Å. The Li(4)-F(3) bond length is 1.97 Å. The Li(4)-F(6) bond length is 1.99 Å. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one F(13), one F(16), one F(17), one F(5), and one F(7) atom. The Li(5)-F(13) bond length is 2.03 Å. The Li(5)-F(16) bond length is 2.49 Å. The Li(5)-F(17) bond length is 1.87 Å. The Li(5)-F(5) bond length is 2.08 Å. The Li(5)-F(7) bond length is 1.91 Å. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(1), one F(10), one F(13), one F(15), one F(19), and one F(8) atom. The Li(6)-O(1) bond length is 2.05 Å. The Li(6)-F(10) bond length is 2.34 Å. The Li(6)-F(13) bond length is 2.37 Å. The Li(6)-F(15) bond length is 2.03 Å. The Li(6)-F(19) bond length is 1.95 Å. The Li(6)-F(8) bond length is 2.05 Å. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one F(12), one F(15), one F(19), one F(20), and one F(4) atom. The Li(7)-F(12) bond length is 2.15 Å. The Li(7)-F(15) bond length is 1.90 Å. The Li(7)-F(19) bond length is 1.84 Å. The Li(7)-F(20) bond length is 2.47 Å. The Li(7)-F(4) bond length is 2.07 Å. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one O(2), one F(11), one F(14), one F(18), one F(21), and one F(3) atom. The Li(8)-O(2) bond length is 1.96 Å. The Li(8)-F(11) bond length is 2.12 Å. The Li(8)-F(14) bond length is 1.89 Å. The Li(8)-F(18) bond length is 2.04 Å. The Li(8)-F(21) bond length is 2.48 Å. The Li(8)-F(3) bond length is 2.52 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(10), one F(13), one F(2), one F(5), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(5)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. The V(1)-O(1) bond length is 1.89 Å. The V(1)-F(10) bond length is 2.09 Å. The V(1)-F(13) bond length is 2.15 Å. The V(1)-F(2) bond length is 2.04 Å. The V(1)-F(5) bond length is 1.94 Å. The V(1)-F(8) bond length is 1.97 Å. In the second V site, V(2) is bonded to one F(12), one F(20), one F(22), one F(4), one F(6), and one F(9) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. The V(2)-F(12) bond length is 2.01 Å. The V(2)-F(20) bond length is 1.98 Å. The V(2)-F(22) bond length is 2.04 Å. The V(2)-F(4) bond length is 1.92 Å. The V(2)-F(6) bond length is 1.93 Å. The V(2)-F(9) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(2), one F(1), one F(11), one F(14), one F(21), and one F(7) atom to form VOF5 octahedra that share corners with four equivalent V(4)OF5 octahedra and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-47°. The V(3)-O(2) bond length is 1.90 Å. The V(3)-F(1) bond length is 2.07 Å. The V(3)-F(11) bond length is 2.05 Å. The V(3)-F(14) bond length is 1.99 Å. The V(3)-F(21) bond length is 2.08 Å. The V(3)-F(7) bond length is 1.95 Å. In the fourth V site, V(4) is bonded to one O(2), one F(1), one F(11), one F(17), one F(21), and one F(3) atom to form VOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-47°. The V(4)-O(2) bond length is 1.89 Å. The V(4)-F(1) bond length is 2.07 Å. The V(4)-F(11) bond length is 2.06 Å. The V(4)-F(17) bond length is 1.89 Å. The V(4)-F(21) bond length is 2.08 Å. The V(4)-F(3) bond length is 2.05 Å. In the fifth V site, V(5) is bonded to one O(1), one F(10), one F(13), one F(16), one F(19), and one F(2) atom to form VOF5 octahedra that share corners with four equivalent V(1)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. The V(5)-O(1) bond length is 1.90 Å. The V(5)-F(10) bond length is 2.07 Å. The V(5)-F(13) bond length is 2.07 Å. The V(5)-F(16) bond length is 1.91 Å. The V(5)-F(19) bond length is 2.06 Å. The V(5)-F(2) bond length is 2.03 Å. In the sixth V site, V(6) is bonded to one F(12), one F(15), one F(18), one F(20), one F(22), and one F(9) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. The V(6)-F(12) bond length is 2.09 Å. The V(6)-F(15) bond length is 1.93 Å. The V(6)-F(18) bond length is 1.92 Å. The V(6)-F(20) bond length is 2.07 Å. The V(6)-F(22) bond length is 1.96 Å. The V(6)-F(9) bond length is 1.98 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Li(6), one V(1), and one V(5) atom. In the second O site, O(2) is bonded in a distorted tetrahedral geometry to one Li(4), one Li(8), 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 3-coordinate geometry to one Li(1), one Li(4), one V(3), and one V(4) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(2), one V(1), and one V(5) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), one Li(8), and one V(4) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(2), one Li(7), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(5), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(5), and one V(3) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(2), one Li(6), and one V(1) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one V(6) atom. In the tenth F site, F(10) is bonded to one Li(2), one Li(6), one V(1), and one V(5) atom to form distorted corner-sharing FLi2V2 trigonal pyramids. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one Li(8), one V(3), and one V(4) atom. In the twelfth F site, F(12) is bonded in a trigonal planar geometry to one Li(7), one V(2), and one V(6) atom. In the thirteenth F site, F(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), one Li(6), one V(1), and one V(5) atom. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(4), one Li(8), and one V(3) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal non-coplanar geometry to one Li(6), one Li(7), and one V(6) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Li(5), and one V(5) atom. In the seventeenth F site, F(17) is bonded in a bent 120 degrees geometry to one Li(5) and one V(4) atom. In the eighteenth F site, F(18) is bonded in a T-shaped geometry to one Li(3), one Li(8), and one V(6) atom. In the nineteenth F site, F(19) is bonded to one Li(2), one Li(6), one Li(7), and one V(5) atom to form distorted corner-sharing FLi3V trigonal pyramids. In the twentieth F site, F(20) is bonded in a 3-coordinate geometry to one Li(7), one V(2), and one V(6) atom. In the twenty-first F site, F(21) is bonded in a 4-coordinate geometry to one Li(4), one Li(8), one V(3), and one V(4) atom. In the twenty-second F site, F(22) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(6) atom.