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 3-coordinate geometry to one F(4), one F(7), and one F(9) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one F(13), one F(5), and one F(8) atom. In the third Li site, Li(3) is bonded to one O(3), one F(15), one F(16), and one F(6) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(2)O2F4 octahedra,  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(6)O2F4 octahedra, and  an edgeedge with one V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-69°. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(5), one F(13), one F(18), and one F(8) atom. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(4), one F(15), one F(3), and one F(6) 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 and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. 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  a cornercorner with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-28°. 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 corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 21-33°. 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  a cornercorner with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. 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 corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 21-33°. 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  a cornercorner with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-28°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(5), one V(2), and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(4), 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 bent 150 degrees geometry to one V(3) and one V(5) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Li(5) and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one V(2) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(2) atom. In the seventh F site, F(7) is bonded in a water-like geometry to one Li(1) and one V(1) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(3) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) 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 bent 150 degrees geometry to one V(3) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(6) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one V(4) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(1) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 150 degrees geometry to one Li(3) and one V(6) atom. In the seventeenth F site, F(17) is bonded in a single-bond geometry to one V(5) atom. In the eighteenth F site, F(18) is bonded in a distorted bent 150 degrees geometry to one Li(4) and one V(5) atom. In the nineteenth F site, F(19) is bonded in a 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 3-coordinate geometry to one F(4), one F(7), and one F(9) atom. The Li(1)-F(4) bond length is 1.86 Å. The Li(1)-F(7) bond length is 1.87 Å. The Li(1)-F(9) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one F(13), one F(5), and one F(8) atom. The Li(2)-O(2) bond length is 2.24 Å. The Li(2)-F(13) bond length is 1.88 Å. The Li(2)-F(5) bond length is 1.85 Å. The Li(2)-F(8) bond length is 1.97 Å. In the third Li site, Li(3) is bonded to one O(3), one F(15), one F(16), and one F(6) atom to form distorted LiOF3 tetrahedra that share  a cornercorner with one V(2)O2F4 octahedra,  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(6)O2F4 octahedra, and  an edgeedge with one V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-69°. The Li(3)-O(3) bond length is 2.06 Å. The Li(3)-F(15) bond length is 1.96 Å. The Li(3)-F(16) bond length is 1.86 Å. The Li(3)-F(6) bond length is 1.93 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(5), one F(13), one F(18), and one F(8) atom. The Li(4)-O(5) bond length is 2.12 Å. The Li(4)-F(13) bond length is 1.97 Å. The Li(4)-F(18) bond length is 1.96 Å. The Li(4)-F(8) bond length is 1.91 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(4), one F(15), one F(3), and one F(6) atom. The Li(5)-O(4) bond length is 2.27 Å. The Li(5)-F(15) bond length is 1.88 Å. The Li(5)-F(3) bond length is 1.84 Å. The Li(5)-F(6) bond length is 1.99 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 and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. The V(1)-O(1) bond length is 1.71 Å. The V(1)-O(3) bond length is 1.96 Å. The V(1)-F(15) bond length is 1.97 Å. The V(1)-F(19) bond length is 2.04 Å. The V(1)-F(7) bond length is 1.88 Å. The V(1)-F(9) bond length is 2.02 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  a cornercorner with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-28°. The V(2)-O(4) bond length is 1.97 Å. The V(2)-O(5) bond length is 1.72 Å. The V(2)-F(10) bond length is 2.09 Å. The V(2)-F(11) bond length is 1.96 Å. The V(2)-F(5) bond length is 1.92 Å. The V(2)-F(6) bond length is 1.92 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 corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 21-33°. The V(3)-O(2) bond length is 1.73 Å. The V(3)-F(1) bond length is 1.97 Å. The V(3)-F(12) bond length is 1.97 Å. The V(3)-F(2) bond length is 2.04 Å. The V(3)-F(4) bond length is 1.84 Å. The V(3)-F(8) bond length is 1.96 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  a cornercorner with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 25-33°. The V(4)-O(1) bond length is 1.94 Å. The V(4)-O(3) bond length is 1.73 Å. The V(4)-F(14) bond length is 1.84 Å. The V(4)-F(19) bond length is 1.99 Å. The V(4)-F(3) bond length is 1.92 Å. The V(4)-F(9) bond length is 2.12 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 corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 21-33°. The V(5)-O(2) bond length is 1.94 Å. The V(5)-F(1) bond length is 1.95 Å. The V(5)-F(12) bond length is 1.93 Å. The V(5)-F(17) bond length is 1.74 Å. The V(5)-F(18) bond length is 1.86 Å. The V(5)-F(2) bond length is 1.97 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  a cornercorner with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 24-28°. The V(6)-O(4) bond length is 1.71 Å. The V(6)-O(5) bond length is 2.00 Å. The V(6)-F(10) bond length is 1.96 Å. The V(6)-F(11) bond length is 2.06 Å. The V(6)-F(13) bond length is 1.97 Å. The V(6)-F(16) bond length is 1.88 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(5), one V(2), and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(4), 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 bent 150 degrees geometry to one V(3) and one V(5) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Li(5) and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one V(2) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(2) atom. In the seventh F site, F(7) is bonded in a water-like geometry to one Li(1) and one V(1) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(3) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) 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 bent 150 degrees geometry to one V(3) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(6) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one V(4) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(1) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 150 degrees geometry to one Li(3) and one V(6) atom. In the seventeenth F site, F(17) is bonded in a single-bond geometry to one V(5) atom. In the eighteenth F site, F(18) is bonded in a distorted bent 150 degrees geometry to one Li(4) and one V(5) atom. In the nineteenth F site, F(19) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom.