LiV2OF5 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(3), one F(13), one F(14), and one F(15) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(4), one F(12), one F(16), one F(19), and one F(7) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one F(1), one F(16), and one F(2) atom. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(2), one F(17), one F(3), one F(5), and one F(6) atom. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(18), one F(2), one F(4), and one F(7) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 34-45°. In the second V site, V(2) is bonded to one O(1), one F(11), one F(14), one F(18), one F(4), and one F(8) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 32-41°. In the third V site, V(3) is bonded to one O(3), one F(11), one F(14), one F(15), one F(8), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 30-39°. In the fourth V site, V(4) is bonded to one O(2), one F(10), one F(12), one F(17), one F(19), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 31-45°. In the fifth V site, V(5) is bonded to one O(2), one F(10), one F(13), one F(17), one F(3), and one F(5) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. In the sixth V site, V(6) is bonded to one O(4), one F(1), one F(16), one F(2), one F(20), and one F(7) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 32-45°. In the seventh V site, V(7) is bonded to one O(3), one F(13), one F(15), one F(3), one F(5), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. In the eighth V site, V(8) is bonded to one O(4), one F(12), one F(16), one F(19), one F(20), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 32-45°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(4), one V(4), and one V(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one V(7) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one V(6), and one V(8) atom. There are twenty inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(3), one V(1), and one V(6) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(6) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(4), one V(5), and one V(7) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(4), one V(5), and one V(7) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(4), one V(4), and one V(8) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(6) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(7) atom. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to one V(4) 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(3) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(2), one V(4), and one V(8) atom. In the thirteenth F site, F(13) is bonded in a trigonal planar geometry to one Li(1), one V(5), and one V(7) atom. In the fourteenth F site, F(14) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the fifteenth F site, F(15) is bonded in a T-shaped geometry to one Li(1), one V(3), and one V(7) atom. In the sixteenth F site, F(16) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one V(6), and one V(8) atom. In the seventeenth F site, F(17) is bonded in a T-shaped geometry to one Li(4), one V(4), and one V(5) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the nineteenth F site, F(19) is bonded in a T-shaped geometry to one Li(2), one V(4), and one V(8) atom. In the twentieth F site, F(20) is bonded in a distorted bent 150 degrees geometry to one V(6) and one V(8) atom.
LiV2OF5 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(3), one F(13), one F(14), and one F(15) atom. The Li(1)-O(3) bond length is 1.97 Å. The Li(1)-F(13) bond length is 1.99 Å. The Li(1)-F(14) bond length is 1.92 Å. The Li(1)-F(15) bond length is 2.16 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(4), one F(12), one F(16), one F(19), and one F(7) atom. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-F(12) bond length is 1.98 Å. The Li(2)-F(16) bond length is 2.35 Å. The Li(2)-F(19) bond length is 2.18 Å. The Li(2)-F(7) bond length is 1.96 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one F(1), one F(16), and one F(2) atom. The Li(3)-O(1) bond length is 1.90 Å. The Li(3)-F(1) bond length is 2.20 Å. The Li(3)-F(16) bond length is 2.04 Å. The Li(3)-F(2) bond length is 1.97 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(2), one F(17), one F(3), one F(5), and one F(6) atom. The Li(4)-O(2) bond length is 2.00 Å. The Li(4)-F(17) bond length is 2.15 Å. The Li(4)-F(3) bond length is 2.12 Å. The Li(4)-F(5) bond length is 1.96 Å. The Li(4)-F(6) bond length is 2.01 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(18), one F(2), one F(4), and one F(7) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 34-45°. The V(1)-O(1) bond length is 1.85 Å. The V(1)-F(1) bond length is 2.12 Å. The V(1)-F(18) bond length is 2.00 Å. The V(1)-F(2) bond length is 2.08 Å. The V(1)-F(4) bond length is 1.93 Å. The V(1)-F(7) bond length is 2.15 Å. In the second V site, V(2) is bonded to one O(1), one F(11), one F(14), one F(18), one F(4), and one F(8) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 32-41°. The V(2)-O(1) bond length is 1.89 Å. The V(2)-F(11) bond length is 2.00 Å. The V(2)-F(14) bond length is 2.07 Å. The V(2)-F(18) bond length is 1.99 Å. The V(2)-F(4) bond length is 2.03 Å. The V(2)-F(8) bond length is 2.01 Å. In the third V site, V(3) is bonded to one O(3), one F(11), one F(14), one F(15), one F(8), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 30-39°. The V(3)-O(3) bond length is 1.88 Å. The V(3)-F(11) bond length is 1.98 Å. The V(3)-F(14) bond length is 2.06 Å. The V(3)-F(15) bond length is 2.06 Å. The V(3)-F(8) bond length is 1.97 Å. The V(3)-F(9) bond length is 2.01 Å. In the fourth V site, V(4) is bonded to one O(2), one F(10), one F(12), one F(17), one F(19), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 31-45°. The V(4)-O(2) bond length is 1.85 Å. The V(4)-F(10) bond length is 1.95 Å. The V(4)-F(12) bond length is 2.05 Å. The V(4)-F(17) bond length is 2.06 Å. The V(4)-F(19) bond length is 2.06 Å. The V(4)-F(6) bond length is 2.10 Å. In the fifth V site, V(5) is bonded to one O(2), one F(10), one F(13), one F(17), one F(3), and one F(5) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. The V(5)-O(2) bond length is 1.85 Å. The V(5)-F(10) bond length is 2.04 Å. The V(5)-F(13) bond length is 2.01 Å. The V(5)-F(17) bond length is 2.00 Å. The V(5)-F(3) bond length is 2.05 Å. The V(5)-F(5) bond length is 2.08 Å. In the sixth V site, V(6) is bonded to one O(4), one F(1), one F(16), one F(2), one F(20), and one F(7) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 32-45°. The V(6)-O(4) bond length is 1.87 Å. The V(6)-F(1) bond length is 1.97 Å. The V(6)-F(16) bond length is 2.10 Å. The V(6)-F(2) bond length is 2.05 Å. The V(6)-F(20) bond length is 2.01 Å. The V(6)-F(7) bond length is 2.06 Å. In the seventh V site, V(7) is bonded to one O(3), one F(13), one F(15), one F(3), one F(5), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. The V(7)-O(3) bond length is 1.84 Å. The V(7)-F(13) bond length is 2.15 Å. The V(7)-F(15) bond length is 1.95 Å. The V(7)-F(3) bond length is 2.09 Å. The V(7)-F(5) bond length is 2.04 Å. The V(7)-F(9) bond length is 2.04 Å. In the eighth V site, V(8) is bonded to one O(4), one F(12), one F(16), one F(19), one F(20), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 32-45°. The V(8)-O(4) bond length is 1.85 Å. The V(8)-F(12) bond length is 2.06 Å. The V(8)-F(16) bond length is 2.08 Å. The V(8)-F(19) bond length is 2.04 Å. The V(8)-F(20) bond length is 2.01 Å. The V(8)-F(6) bond length is 2.02 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(4), one V(4), and one V(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one V(7) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one V(6), and one V(8) atom. There are twenty inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(3), one V(1), and one V(6) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(6) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(4), one V(5), and one V(7) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(4), one V(5), and one V(7) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(4), one V(4), and one V(8) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(6) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(7) atom. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to one V(4) 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(3) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(2), one V(4), and one V(8) atom. In the thirteenth F site, F(13) is bonded in a trigonal planar geometry to one Li(1), one V(5), and one V(7) atom. In the fourteenth F site, F(14) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the fifteenth F site, F(15) is bonded in a T-shaped geometry to one Li(1), one V(3), and one V(7) atom. In the sixteenth F site, F(16) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one V(6), and one V(8) atom. In the seventeenth F site, F(17) is bonded in a T-shaped geometry to one Li(4), one V(4), and one V(5) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the nineteenth F site, F(19) is bonded in a T-shaped geometry to one Li(2), one V(4), and one V(8) atom. In the twentieth F site, F(20) is bonded in a distorted bent 150 degrees geometry to one V(6) and one V(8) atom.