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 4-coordinate geometry to one O(2), one F(14), one F(17), and one F(4) atom. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one F(15), one F(2), and one F(5) atom. In the third Li site, Li(3) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one F(16), one F(3), and one F(6) atom. In the fourth Li site, Li(4) is bonded in a distorted trigonal non-coplanar geometry to one F(12), one F(15), and one F(5) atom. In the fifth Li site, Li(5) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one F(13), one F(16), and one F(6) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one F(10), one F(19), one F(3), and one F(5) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. In the second V site, V(2) is bonded to one O(1), one O(4), one F(1), one F(11), one F(4), and one F(6) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-38°. In the third V site, V(3) is bonded to one O(2), one F(12), one F(18), one F(7), one F(8), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. In the fourth V site, V(4) is bonded to one O(3), one O(5), one F(10), one F(13), one F(15), and one F(19) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. In the fifth V site, V(5) is bonded to one O(1), one O(4), one F(1), one F(11), one F(14), and one F(16) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-38°. In the sixth V site, V(6) is bonded to one O(2), one F(17), one F(18), one F(2), one F(8), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one V(2), and one V(5) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(3), and one V(6) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one V(1) and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(5) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one V(1) and one V(4) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one V(2) and one V(5) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(6) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(3) and one V(1) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(1) atom. In the sixth F site, F(6) is bonded in a trigonal non-coplanar geometry to one Li(3), one Li(5), and one V(2) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the tenth F site, F(10) is bonded in a distorted 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 bent 150 degrees geometry to one V(2) and one V(5) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(4) and one V(3) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(5) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(1) and one V(5) atom. In the fifteenth F site, F(15) is bonded in a trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(4) atom. In the sixteenth F site, F(16) is bonded in a trigonal non-coplanar geometry to one Li(3), 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(1) and one V(6) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the nineteenth F site, F(19) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) 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 4-coordinate geometry to one O(2), one F(14), one F(17), and one F(4) atom. The Li(1)-O(2) bond length is 2.32 Å. The Li(1)-F(14) bond length is 1.86 Å. The Li(1)-F(17) bond length is 1.94 Å. The Li(1)-F(4) bond length is 1.86 Å. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one F(15), one F(2), and one F(5) atom. The Li(2)-F(15) bond length is 1.94 Å. The Li(2)-F(2) bond length is 1.84 Å. The Li(2)-F(5) bond length is 1.91 Å. In the third Li site, Li(3) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one F(16), one F(3), and one F(6) atom. The Li(3)-O(1) bond length is 2.57 Å. The Li(3)-F(16) bond length is 1.93 Å. The Li(3)-F(3) bond length is 1.87 Å. The Li(3)-F(6) bond length is 1.90 Å. In the fourth Li site, Li(4) is bonded in a distorted trigonal non-coplanar geometry to one F(12), one F(15), and one F(5) atom. The Li(4)-F(12) bond length is 1.92 Å. The Li(4)-F(15) bond length is 1.90 Å. The Li(4)-F(5) bond length is 1.92 Å. In the fifth Li site, Li(5) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one F(13), one F(16), and one F(6) atom. The Li(5)-O(1) bond length is 2.55 Å. The Li(5)-F(13) bond length is 1.87 Å. The Li(5)-F(16) bond length is 1.90 Å. The Li(5)-F(6) bond length is 1.93 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one F(10), one F(19), one F(3), and one F(5) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(5) bond length is 1.71 Å. The V(1)-F(10) bond length is 2.12 Å. The V(1)-F(19) bond length is 1.96 Å. The V(1)-F(3) bond length is 1.86 Å. The V(1)-F(5) bond length is 1.97 Å. In the second V site, V(2) is bonded to one O(1), one O(4), one F(1), one F(11), one F(4), and one F(6) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-38°. The V(2)-O(1) bond length is 1.72 Å. The V(2)-O(4) bond length is 2.01 Å. The V(2)-F(1) bond length is 1.96 Å. The V(2)-F(11) bond length is 2.13 Å. The V(2)-F(4) bond length is 1.87 Å. The V(2)-F(6) bond length is 1.97 Å. In the third V site, V(3) is bonded to one O(2), one F(12), one F(18), one F(7), one F(8), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. The V(3)-O(2) bond length is 1.91 Å. The V(3)-F(12) bond length is 1.84 Å. The V(3)-F(18) bond length is 1.95 Å. The V(3)-F(7) bond length is 1.76 Å. The V(3)-F(8) bond length is 1.93 Å. The V(3)-F(9) bond length is 1.93 Å. In the fourth V site, V(4) is bonded to one O(3), one O(5), one F(10), one F(13), one F(15), and one F(19) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. The V(4)-O(3) bond length is 1.71 Å. The V(4)-O(5) bond length is 2.01 Å. The V(4)-F(10) bond length is 1.96 Å. The V(4)-F(13) bond length is 1.86 Å. The V(4)-F(15) bond length is 1.97 Å. The V(4)-F(19) bond length is 2.13 Å. In the fifth V site, V(5) is bonded to one O(1), one O(4), one F(1), one F(11), one F(14), and one F(16) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-38°. The V(5)-O(1) bond length is 2.02 Å. The V(5)-O(4) bond length is 1.71 Å. The V(5)-F(1) bond length is 2.12 Å. The V(5)-F(11) bond length is 1.97 Å. The V(5)-F(14) bond length is 1.87 Å. The V(5)-F(16) bond length is 1.96 Å. In the sixth V site, V(6) is bonded to one O(2), one F(17), one F(18), one F(2), one F(8), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. The V(6)-O(2) bond length is 1.72 Å. The V(6)-F(17) bond length is 1.86 Å. The V(6)-F(18) bond length is 2.04 Å. The V(6)-F(2) bond length is 1.89 Å. The V(6)-F(8) bond length is 1.96 Å. The V(6)-F(9) bond length is 1.97 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one V(2), and one V(5) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(3), and one V(6) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one V(1) and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(5) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one V(1) and one V(4) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one V(2) and one V(5) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(6) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(3) and one V(1) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(1) atom. In the sixth F site, F(6) is bonded in a trigonal non-coplanar geometry to one Li(3), one Li(5), and one V(2) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the tenth F site, F(10) is bonded in a distorted 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 bent 150 degrees geometry to one V(2) and one V(5) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(4) and one V(3) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(5) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(1) and one V(5) atom. In the fifteenth F site, F(15) is bonded in a trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(4) atom. In the sixteenth F site, F(16) is bonded in a trigonal non-coplanar geometry to one Li(3), 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(1) and one V(6) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the nineteenth F site, F(19) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom.