LiV2(OF)3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(4), one O(8), one O(9), one F(3), one F(5), and one F(8) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(6), one F(1), one F(3), and one F(8) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(7), one F(6), one F(7), and one F(9) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(8), one O(9), one F(2), one F(4), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-35°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(6), one F(1), one F(6), and one F(7) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 17-49°. In the third V site, V(3) is bonded to one O(1), one O(5), one O(7), one F(2), one F(4), and one F(9) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-41°. In the fourth V site, V(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(3), and one F(8) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 33-49°. In the fifth V site, V(5) is bonded to one O(3), one O(5), one O(7), one F(6), one F(7), and one F(9) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 17-41°. In the sixth V site, V(6) is bonded to one O(4), one O(8), one O(9), one F(3), one F(5), and one F(8) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 25-40°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Li(3), one V(2), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(4), and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(3), one V(3), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(6) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one V(4), and one V(6) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(6) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(5) atom. In the seventh F site, F(7) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(5) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(4), and one V(6) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom.
LiV2(OF)3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(4), one O(8), one O(9), one F(3), one F(5), and one F(8) atom. The Li(1)-O(4) bond length is 2.00 Å. The Li(1)-O(8) bond length is 2.45 Å. The Li(1)-O(9) bond length is 2.29 Å. The Li(1)-F(3) bond length is 2.01 Å. The Li(1)-F(5) bond length is 2.15 Å. The Li(1)-F(8) bond length is 2.11 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(6), one F(1), one F(3), and one F(8) atom. The Li(2)-O(2) bond length is 2.04 Å. The Li(2)-O(4) bond length is 2.20 Å. The Li(2)-O(6) bond length is 2.03 Å. The Li(2)-F(1) bond length is 2.01 Å. The Li(2)-F(3) bond length is 2.15 Å. The Li(2)-F(8) bond length is 2.41 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(7), one F(6), one F(7), and one F(9) atom. The Li(3)-O(3) bond length is 2.55 Å. The Li(3)-O(5) bond length is 2.01 Å. The Li(3)-O(7) bond length is 2.13 Å. The Li(3)-F(6) bond length is 2.24 Å. The Li(3)-F(7) bond length is 2.23 Å. The Li(3)-F(9) bond length is 2.00 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(8), one O(9), one F(2), one F(4), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-35°. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(8) bond length is 1.73 Å. The V(1)-O(9) bond length is 1.93 Å. The V(1)-F(2) bond length is 2.01 Å. The V(1)-F(4) bond length is 1.95 Å. The V(1)-F(5) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(6), one F(1), one F(6), and one F(7) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 17-49°. The V(2)-O(2) bond length is 1.85 Å. The V(2)-O(3) bond length is 2.04 Å. The V(2)-O(6) bond length is 2.03 Å. The V(2)-F(1) bond length is 2.06 Å. The V(2)-F(6) bond length is 1.98 Å. The V(2)-F(7) bond length is 2.05 Å. In the third V site, V(3) is bonded to one O(1), one O(5), one O(7), one F(2), one F(4), and one F(9) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-41°. The V(3)-O(1) bond length is 1.72 Å. The V(3)-O(5) bond length is 1.97 Å. The V(3)-O(7) bond length is 1.99 Å. The V(3)-F(2) bond length is 2.01 Å. The V(3)-F(4) bond length is 2.02 Å. The V(3)-F(9) bond length is 1.99 Å. In the fourth V site, V(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(3), and one F(8) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 33-49°. The V(4)-O(2) bond length is 1.87 Å. The V(4)-O(4) bond length is 2.02 Å. The V(4)-O(6) bond length is 1.71 Å. The V(4)-F(1) bond length is 2.03 Å. The V(4)-F(3) bond length is 2.02 Å. The V(4)-F(8) bond length is 2.25 Å. In the fifth V site, V(5) is bonded to one O(3), one O(5), one O(7), one F(6), one F(7), and one F(9) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 17-41°. The V(5)-O(3) bond length is 1.68 Å. The V(5)-O(5) bond length is 1.79 Å. The V(5)-O(7) bond length is 1.74 Å. The V(5)-F(6) bond length is 2.10 Å. The V(5)-F(7) bond length is 2.04 Å. The V(5)-F(9) bond length is 2.21 Å. In the sixth V site, V(6) is bonded to one O(4), one O(8), one O(9), one F(3), one F(5), and one F(8) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 25-40°. The V(6)-O(4) bond length is 1.83 Å. The V(6)-O(8) bond length is 1.90 Å. The V(6)-O(9) bond length is 1.77 Å. The V(6)-F(3) bond length is 2.26 Å. The V(6)-F(5) bond length is 2.01 Å. The V(6)-F(8) bond length is 2.02 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Li(3), one V(2), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(4), and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(3), one V(3), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(6) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one V(4), and one V(6) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(6) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(5) atom. In the seventh F site, F(7) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(5) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(4), and one V(6) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom.