Li5V6O5F19 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(5), one F(15), one F(19), one F(3), and one F(8) atom. In the second Li site, Li(2) is bonded to one O(3), one F(13), one F(14), and one F(7) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(6)OF5 octahedra, and  an edgeedge with one V(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 41-75°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(5), one F(10), one F(12), one F(15), and one F(8) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(12), one F(15), one F(18), and one F(3) atom. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(1), one F(16), one F(17), one F(4), and one F(6) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), one F(10), one F(19), one F(4), and one F(8) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 32-35°. In the second V site, V(2) is bonded to one O(1), one F(11), one F(2), one F(6), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent V(6)OF5 octahedra and  a cornercorner with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. In the third V site, V(3) is bonded to one O(3), one O(4), one F(1), one F(13), one F(18), and one F(3) atom to form distorted VO2F4 octahedra that share corners with four equivalent V(4)O2F4 octahedra and  an edgeedge with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-40°. In the fourth V site, V(4) is bonded to one O(3), one O(4), one F(1), one F(12), one F(18), and one F(5) atom to form distorted VO2F4 octahedra that share corners with four equivalent V(3)O2F4 octahedra and  a cornercorner with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-40°. In the fifth V site, V(5) is bonded to one O(2), one O(5), one F(10), one F(15), one F(16), and one F(19) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 32-35°. In the sixth V site, V(6) is bonded to one O(1), one F(11), one F(14), one F(17), one F(2), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent V(2)OF5 octahedra and  a cornercorner with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(5), one V(2), and one V(6) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(5) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(4), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(5) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(1), one Li(4), and one V(3) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(5) and one V(1) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(4) atom. In the sixth F site, F(6) is bonded in an L-shaped geometry to one Li(5) and one V(2) atom. In the seventh F site, F(7) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one V(2) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(3), and one V(1) 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 distorted T-shaped geometry to one Li(3), one V(1), and one V(5) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(4) atom. In the thirteenth F site, F(13) is bonded in a water-like geometry to one Li(2) and one V(3) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(2) and one V(6) atom. In the fifteenth F site, F(15) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(3), one Li(4), and one V(5) atom. In the sixteenth F site, F(16) is bonded in a bent 150 degrees geometry to one Li(5) and one V(5) atom. In the seventeenth F site, F(17) is bonded in a water-like geometry to one Li(5) and one V(6) atom. In the eighteenth F site, F(18) is bonded in a distorted T-shaped geometry to one Li(4), one V(3), and one V(4) atom. In the nineteenth F site, F(19) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(5) atom.
Li5V6O5F19 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(5), one F(15), one F(19), one F(3), and one F(8) atom. The Li(1)-O(2) bond length is 2.32 Å. The Li(1)-O(5) bond length is 2.42 Å. The Li(1)-F(15) bond length is 2.15 Å. The Li(1)-F(19) bond length is 2.22 Å. The Li(1)-F(3) bond length is 1.84 Å. The Li(1)-F(8) bond length is 1.92 Å. In the second Li site, Li(2) is bonded to one O(3), one F(13), one F(14), and one F(7) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(6)OF5 octahedra, and  an edgeedge with one V(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 41-75°. The Li(2)-O(3) bond length is 2.16 Å. The Li(2)-F(13) bond length is 1.92 Å. The Li(2)-F(14) bond length is 1.98 Å. The Li(2)-F(7) bond length is 1.85 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(5), one F(10), one F(12), one F(15), and one F(8) atom. The Li(3)-O(2) bond length is 2.54 Å. The Li(3)-O(5) bond length is 2.58 Å. The Li(3)-F(10) bond length is 2.40 Å. The Li(3)-F(12) bond length is 1.83 Å. The Li(3)-F(15) bond length is 1.97 Å. The Li(3)-F(8) bond length is 1.94 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(12), one F(15), one F(18), and one F(3) atom. The Li(4)-O(3) bond length is 2.24 Å. The Li(4)-O(4) bond length is 2.20 Å. The Li(4)-F(12) bond length is 1.93 Å. The Li(4)-F(15) bond length is 2.04 Å. The Li(4)-F(18) bond length is 2.22 Å. The Li(4)-F(3) bond length is 2.06 Å. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(1), one F(16), one F(17), one F(4), and one F(6) atom. The Li(5)-O(1) bond length is 2.10 Å. The Li(5)-F(16) bond length is 1.91 Å. The Li(5)-F(17) bond length is 2.04 Å. The Li(5)-F(4) bond length is 1.90 Å. The Li(5)-F(6) bond length is 2.36 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), one F(10), one F(19), one F(4), and one F(8) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 32-35°. The V(1)-O(2) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.72 Å. The V(1)-F(10) bond length is 2.17 Å. The V(1)-F(19) bond length is 1.98 Å. The V(1)-F(4) bond length is 1.85 Å. The V(1)-F(8) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(1), one F(11), one F(2), one F(6), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent V(6)OF5 octahedra and  a cornercorner with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. The V(2)-O(1) bond length is 1.73 Å. The V(2)-F(11) bond length is 2.07 Å. The V(2)-F(2) bond length is 1.97 Å. The V(2)-F(6) bond length is 1.85 Å. The V(2)-F(7) bond length is 1.88 Å. The V(2)-F(9) bond length is 1.99 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one F(1), one F(13), one F(18), and one F(3) atom to form distorted VO2F4 octahedra that share corners with four equivalent V(4)O2F4 octahedra and  an edgeedge with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-40°. The V(3)-O(3) bond length is 2.21 Å. The V(3)-O(4) bond length is 1.70 Å. The V(3)-F(1) bond length is 1.98 Å. The V(3)-F(13) bond length is 1.86 Å. The V(3)-F(18) bond length is 1.99 Å. The V(3)-F(3) bond length is 1.97 Å. In the fourth V site, V(4) is bonded to one O(3), one O(4), one F(1), one F(12), one F(18), and one F(5) atom to form distorted VO2F4 octahedra that share corners with four equivalent V(3)O2F4 octahedra and  a cornercorner with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-40°. The V(4)-O(3) bond length is 1.71 Å. The V(4)-O(4) bond length is 2.17 Å. The V(4)-F(1) bond length is 1.97 Å. The V(4)-F(12) bond length is 2.02 Å. The V(4)-F(18) bond length is 2.00 Å. The V(4)-F(5) bond length is 1.82 Å. In the fifth V site, V(5) is bonded to one O(2), one O(5), one F(10), one F(15), one F(16), and one F(19) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 32-35°. The V(5)-O(2) bond length is 1.73 Å. The V(5)-O(5) bond length is 2.02 Å. The V(5)-F(10) bond length is 1.97 Å. The V(5)-F(15) bond length is 2.01 Å. The V(5)-F(16) bond length is 1.84 Å. The V(5)-F(19) bond length is 2.10 Å. In the sixth V site, V(6) is bonded to one O(1), one F(11), one F(14), one F(17), one F(2), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent V(2)OF5 octahedra and  a cornercorner with one Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. The V(6)-O(1) bond length is 1.94 Å. The V(6)-F(11) bond length is 1.92 Å. The V(6)-F(14) bond length is 1.81 Å. The V(6)-F(17) bond length is 1.81 Å. The V(6)-F(2) bond length is 1.93 Å. The V(6)-F(9) bond length is 1.93 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(5), one V(2), and one V(6) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(5) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(4), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(5) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(1), one Li(4), and one V(3) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(5) and one V(1) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(4) atom. In the sixth F site, F(6) is bonded in an L-shaped geometry to one Li(5) and one V(2) atom. In the seventh F site, F(7) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one V(2) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(3), and one V(1) 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 distorted T-shaped geometry to one Li(3), one V(1), and one V(5) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(4) atom. In the thirteenth F site, F(13) is bonded in a water-like geometry to one Li(2) and one V(3) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(2) and one V(6) atom. In the fifteenth F site, F(15) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(3), one Li(4), and one V(5) atom. In the sixteenth F site, F(16) is bonded in a bent 150 degrees geometry to one Li(5) and one V(5) atom. In the seventeenth F site, F(17) is bonded in a water-like geometry to one Li(5) and one V(6) atom. In the eighteenth F site, F(18) is bonded in a distorted T-shaped geometry to one Li(4), one V(3), and one V(4) atom. In the nineteenth F site, F(19) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(5) atom.