Li11V6O5F19 crystallizes in the triclinic P1 space group. There are eleven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(18), one F(2), one F(5), and one F(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(4), one F(10), one F(16), one F(3), and one F(6) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one F(14), one F(4), one F(7), and one F(9) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), one F(15), one F(19), one F(3), and one F(6) atom. In the fifth Li site, Li(5) is bonded to one F(17), one F(2), one F(4), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(1)O2F4 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent Li(8)OF3 trigonal pyramids, and  an edgeedge with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 61-65°. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(5), one F(10), one F(11), one F(13), one F(5), and one F(8) atom. In the seventh Li site, Li(7) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(12), one F(13), one F(18), and one F(8) atom. In the eighth Li site, Li(8) is bonded to one O(1), one F(14), one F(17), and one F(7) atom to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one V(5)OF5 octahedra, corners with two equivalent V(1)O2F4 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-83°. In the ninth Li site, Li(9) is bonded to one O(4), one F(15), one F(16), and one F(6) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(1)O2F4 octahedra, corners with two equivalent V(2)O2F4 octahedra, and corners with two equivalent V(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-82°. In the tenth Li site, Li(10) is bonded in a 4-coordinate geometry to one O(3), one F(15), one F(16), and one F(3) atom. In the eleventh Li site, Li(11) is bonded in a 6-coordinate geometry to one O(4), one O(5), one F(11), one F(13), one F(18), and one F(5) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one F(15), one F(19), one F(7), and one F(9) atom to form VO2F4 octahedra that share corners with four equivalent V(4)O2F4 octahedra,  a cornercorner with one Li(5)F4 tetrahedra,  a cornercorner with one Li(9)OF3 tetrahedra, and corners with two equivalent Li(8)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 40-48°. In the second V site, V(2) is bonded to one O(4), one O(5), one F(10), one F(11), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(6)O2F4 octahedra and corners with two equivalent Li(9)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 41-46°. In the third V site, V(3) is bonded to one O(2), one F(1), one F(12), one F(2), one F(4), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(5)OF5 octahedra and corners with two equivalent Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. In the fourth V site, V(4) is bonded to one O(1), one O(3), one F(14), one F(19), one F(3), and one F(9) atom to form VO2F4 octahedra that share corners with four equivalent V(1)O2F4 octahedra and corners with two equivalent Li(8)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 40-48°. In the fifth V site, V(5) is bonded to one O(2), one F(1), one F(12), one F(17), one F(18), and one F(2) atom to form VOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra,  a cornercorner with one Li(8)OF3 trigonal pyramid, and  an edgeedge with one Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. In the sixth V site, V(6) is bonded to one O(4), one O(5), one F(10), one F(11), one F(13), and one F(16) atom to form VO2F4 octahedra that share corners with four equivalent V(2)O2F4 octahedra and corners with two equivalent Li(9)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 41-46°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(8), one V(1), and one V(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(7), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(10), one Li(4), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(11), one Li(2), one Li(9), one V(2), and one V(6) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(11), one Li(6), one V(2), and one V(6) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(7), one V(3), and one V(5) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(5), one V(3), and one V(5) atom. In the third F site, F(3) is bonded to one Li(10), one Li(2), one Li(4), and one V(4) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(5), and one V(3) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(11), one Li(6), and one V(2) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(2), one Li(4), one Li(9), and one V(2) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the seventh F site, F(7) is bonded to one Li(3), one Li(5), one Li(8), and one V(1) atom to form corner-sharing FLi3V tetrahedra. In the eighth F site, F(8) is bonded to one Li(1), one Li(6), one Li(7), and one V(3) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(4) atom. In the tenth F site, F(10) is bonded in a 4-coordinate geometry to one Li(2), one Li(6), one V(2), and one V(6) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(11), one Li(6), one V(2), and one V(6) atom. In the twelfth F site, F(12) is bonded in a 3-coordinate geometry to one Li(7), one V(3), and one V(5) atom. In the thirteenth F site, F(13) is bonded to one Li(11), one Li(6), one Li(7), and one V(6) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(3), one Li(8), and one V(4) atom. In the fifteenth F site, F(15) is bonded to one Li(10), one Li(4), one Li(9), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the sixteenth F site, F(16) is bonded to one Li(10), one Li(2), one Li(9), and one V(6) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the seventeenth F site, F(17) is bonded in a T-shaped geometry to one Li(5), one Li(8), and one V(5) atom. In the eighteenth F site, F(18) is bonded to one Li(1), one Li(11), one Li(7), and one V(5) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the nineteenth F site, F(19) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one V(4) atom.
Li11V6O5F19 crystallizes in the triclinic P1 space group. There are eleven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(18), one F(2), one F(5), and one F(8) atom. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-F(1) bond length is 2.49 Å. The Li(1)-F(18) bond length is 2.23 Å. The Li(1)-F(2) bond length is 2.32 Å. The Li(1)-F(5) bond length is 1.91 Å. The Li(1)-F(8) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(4), one F(10), one F(16), one F(3), and one F(6) atom. The Li(2)-O(4) bond length is 2.55 Å. The Li(2)-F(10) bond length is 2.04 Å. The Li(2)-F(16) bond length is 2.09 Å. The Li(2)-F(3) bond length is 1.91 Å. The Li(2)-F(6) bond length is 1.95 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one F(14), one F(4), one F(7), and one F(9) atom. The Li(3)-O(1) bond length is 2.48 Å. The Li(3)-F(14) bond length is 1.99 Å. The Li(3)-F(4) bond length is 1.94 Å. The Li(3)-F(7) bond length is 1.99 Å. The Li(3)-F(9) bond length is 2.10 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), one F(15), one F(19), one F(3), and one F(6) atom. The Li(4)-O(1) bond length is 2.56 Å. The Li(4)-O(3) bond length is 2.38 Å. The Li(4)-F(15) bond length is 2.11 Å. The Li(4)-F(19) bond length is 2.01 Å. The Li(4)-F(3) bond length is 1.96 Å. The Li(4)-F(6) bond length is 1.97 Å. In the fifth Li site, Li(5) is bonded to one F(17), one F(2), one F(4), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(1)O2F4 octahedra, corners with two equivalent V(3)OF5 octahedra, corners with two equivalent Li(8)OF3 trigonal pyramids, and  an edgeedge with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 61-65°. The Li(5)-F(17) bond length is 1.99 Å. The Li(5)-F(2) bond length is 2.03 Å. The Li(5)-F(4) bond length is 1.89 Å. The Li(5)-F(7) bond length is 1.90 Å. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(5), one F(10), one F(11), one F(13), one F(5), and one F(8) atom. The Li(6)-O(5) bond length is 1.97 Å. The Li(6)-F(10) bond length is 2.47 Å. The Li(6)-F(11) bond length is 2.55 Å. The Li(6)-F(13) bond length is 2.16 Å. The Li(6)-F(5) bond length is 1.92 Å. The Li(6)-F(8) bond length is 1.95 Å. In the seventh Li site, Li(7) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(12), one F(13), one F(18), and one F(8) atom. The Li(7)-O(2) bond length is 2.49 Å. The Li(7)-F(1) bond length is 2.02 Å. The Li(7)-F(12) bond length is 2.47 Å. The Li(7)-F(13) bond length is 1.89 Å. The Li(7)-F(18) bond length is 1.96 Å. The Li(7)-F(8) bond length is 2.08 Å. In the eighth Li site, Li(8) is bonded to one O(1), one F(14), one F(17), and one F(7) atom to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one V(5)OF5 octahedra, corners with two equivalent V(1)O2F4 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-83°. The Li(8)-O(1) bond length is 2.04 Å. The Li(8)-F(14) bond length is 1.90 Å. The Li(8)-F(17) bond length is 1.91 Å. The Li(8)-F(7) bond length is 2.12 Å. In the ninth Li site, Li(9) is bonded to one O(4), one F(15), one F(16), and one F(6) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(1)O2F4 octahedra, corners with two equivalent V(2)O2F4 octahedra, and corners with two equivalent V(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-82°. The Li(9)-O(4) bond length is 2.00 Å. The Li(9)-F(15) bond length is 1.88 Å. The Li(9)-F(16) bond length is 1.91 Å. The Li(9)-F(6) bond length is 2.19 Å. In the tenth Li site, Li(10) is bonded in a 4-coordinate geometry to one O(3), one F(15), one F(16), and one F(3) atom. The Li(10)-O(3) bond length is 1.98 Å. The Li(10)-F(15) bond length is 1.92 Å. The Li(10)-F(16) bond length is 1.94 Å. The Li(10)-F(3) bond length is 2.14 Å. In the eleventh Li site, Li(11) is bonded in a 6-coordinate geometry to one O(4), one O(5), one F(11), one F(13), one F(18), and one F(5) atom. The Li(11)-O(4) bond length is 2.48 Å. The Li(11)-O(5) bond length is 2.39 Å. The Li(11)-F(11) bond length is 2.02 Å. The Li(11)-F(13) bond length is 1.97 Å. The Li(11)-F(18) bond length is 1.97 Å. The Li(11)-F(5) bond length is 2.11 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one F(15), one F(19), one F(7), and one F(9) atom to form VO2F4 octahedra that share corners with four equivalent V(4)O2F4 octahedra,  a cornercorner with one Li(5)F4 tetrahedra,  a cornercorner with one Li(9)OF3 tetrahedra, and corners with two equivalent Li(8)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 40-48°. The V(1)-O(1) bond length is 1.88 Å. The V(1)-O(3) bond length is 1.94 Å. The V(1)-F(15) bond length is 2.06 Å. The V(1)-F(19) bond length is 2.11 Å. The V(1)-F(7) bond length is 2.08 Å. The V(1)-F(9) bond length is 2.15 Å. In the second V site, V(2) is bonded to one O(4), one O(5), one F(10), one F(11), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(6)O2F4 octahedra and corners with two equivalent Li(9)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 41-46°. The V(2)-O(4) bond length is 1.89 Å. The V(2)-O(5) bond length is 1.94 Å. The V(2)-F(10) bond length is 2.14 Å. The V(2)-F(11) bond length is 2.10 Å. The V(2)-F(5) bond length is 2.07 Å. The V(2)-F(6) bond length is 2.05 Å. In the third V site, V(3) is bonded to one O(2), one F(1), one F(12), one F(2), one F(4), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(5)OF5 octahedra and corners with two equivalent Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. The V(3)-O(2) bond length is 1.90 Å. The V(3)-F(1) bond length is 2.06 Å. The V(3)-F(12) bond length is 1.97 Å. The V(3)-F(2) bond length is 2.07 Å. The V(3)-F(4) bond length is 1.96 Å. The V(3)-F(8) bond length is 2.04 Å. In the fourth V site, V(4) is bonded to one O(1), one O(3), one F(14), one F(19), one F(3), and one F(9) atom to form VO2F4 octahedra that share corners with four equivalent V(1)O2F4 octahedra and corners with two equivalent Li(8)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 40-48°. The V(4)-O(1) bond length is 1.94 Å. The V(4)-O(3) bond length is 1.90 Å. The V(4)-F(14) bond length is 2.00 Å. The V(4)-F(19) bond length is 2.14 Å. The V(4)-F(3) bond length is 2.08 Å. The V(4)-F(9) bond length is 2.13 Å. In the fifth V site, V(5) is bonded to one O(2), one F(1), one F(12), one F(17), one F(18), and one F(2) atom to form VOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra,  a cornercorner with one Li(8)OF3 trigonal pyramid, and  an edgeedge with one Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-46°. The V(5)-O(2) bond length is 1.89 Å. The V(5)-F(1) bond length is 2.08 Å. The V(5)-F(12) bond length is 2.01 Å. The V(5)-F(17) bond length is 1.93 Å. The V(5)-F(18) bond length is 2.03 Å. The V(5)-F(2) bond length is 2.12 Å. In the sixth V site, V(6) is bonded to one O(4), one O(5), one F(10), one F(11), one F(13), and one F(16) atom to form VO2F4 octahedra that share corners with four equivalent V(2)O2F4 octahedra and corners with two equivalent Li(9)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 41-46°. The V(6)-O(4) bond length is 1.92 Å. The V(6)-O(5) bond length is 1.89 Å. The V(6)-F(10) bond length is 2.12 Å. The V(6)-F(11) bond length is 2.13 Å. The V(6)-F(13) bond length is 2.07 Å. The V(6)-F(16) bond length is 2.05 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(8), one V(1), and one V(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(7), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(10), one Li(4), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(11), one Li(2), one Li(9), one V(2), and one V(6) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(11), one Li(6), one V(2), and one V(6) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(7), one V(3), and one V(5) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(5), one V(3), and one V(5) atom. In the third F site, F(3) is bonded to one Li(10), one Li(2), one Li(4), and one V(4) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(5), and one V(3) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(11), one Li(6), and one V(2) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(2), one Li(4), one Li(9), and one V(2) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the seventh F site, F(7) is bonded to one Li(3), one Li(5), one Li(8), and one V(1) atom to form corner-sharing FLi3V tetrahedra. In the eighth F site, F(8) is bonded to one Li(1), one Li(6), one Li(7), and one V(3) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(4) atom. In the tenth F site, F(10) is bonded in a 4-coordinate geometry to one Li(2), one Li(6), one V(2), and one V(6) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(11), one Li(6), one V(2), and one V(6) atom. In the twelfth F site, F(12) is bonded in a 3-coordinate geometry to one Li(7), one V(3), and one V(5) atom. In the thirteenth F site, F(13) is bonded to one Li(11), one Li(6), one Li(7), and one V(6) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(3), one Li(8), and one V(4) atom. In the fifteenth F site, F(15) is bonded to one Li(10), one Li(4), one Li(9), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the sixteenth F site, F(16) is bonded to one Li(10), one Li(2), one Li(9), and one V(6) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the seventeenth F site, F(17) is bonded in a T-shaped geometry to one Li(5), one Li(8), and one V(5) atom. In the eighteenth F site, F(18) is bonded to one Li(1), one Li(11), one Li(7), and one V(5) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the nineteenth F site, F(19) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one V(4) atom.