Li3V2(OF)4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), and one F(1) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(3), one F(1), one F(2), one F(3), and one F(5) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(4), one F(1), one F(2), one F(4), and one F(6) atom. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(5), one F(3), one F(5), one F(7), and one F(8) atom. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(6), one F(4), one F(6), one F(7), and one F(8) atom. In the sixth Li site, Li(6) is bonded to one O(1), one O(3), one O(6), one O(7), one O(8), and one F(7) atom to form distorted LiO5F octahedra that share corners with two equivalent V(4)O4F2 octahedra,  an edgeedge with one V(2)O4F2 octahedra, edges with two equivalent V(3)O4F2 octahedra, and  a faceface with one V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(7), one F(1), and one F(3) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, and  a faceface with one Li(6)O5F octahedra. The corner-sharing octahedral tilt angles range from 30-44°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(8), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, and  an edgeedge with one Li(6)O5F octahedra. The corner-sharing octahedral tilt angles range from 35-44°. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one O(7), one F(5), and one F(7) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, and edges with two equivalent Li(6)O5F octahedra. The corner-sharing octahedral tilt angles range from 30-45°. In the fourth V site, V(4) is bonded to one O(2), one O(5), one O(6), one O(8), one F(6), and one F(8) atom to form distorted VO4F2 octahedra that share corners with two equivalent Li(6)O5F octahedra, corners with two equivalent V(2)O4F2 octahedra, and corners with two equivalent V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-60°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted square co-planar geometry to one Li(1), one Li(6), one V(1), and one V(3) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(6), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(5), one Li(6), one V(3), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(6), one V(1), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(6), one V(2), and one V(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(3) 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(4) atom. In the seventh F site, F(7) is bonded in a distorted tetrahedral geometry to one Li(4), one Li(5), one Li(6), and one V(3) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(4), one Li(5), and one V(4) atom.
Li3V2(OF)4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), and one F(1) atom. The Li(1)-O(1) bond length is 2.16 Å. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-O(4) bond length is 2.02 Å. The Li(1)-O(5) bond length is 2.12 Å. The Li(1)-O(7) bond length is 2.08 Å. The Li(1)-F(1) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(3), one F(1), one F(2), one F(3), and one F(5) atom. The Li(2)-O(3) bond length is 2.46 Å. The Li(2)-F(1) bond length is 2.37 Å. The Li(2)-F(2) bond length is 1.99 Å. The Li(2)-F(3) bond length is 1.99 Å. The Li(2)-F(5) bond length is 1.98 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(4), one F(1), one F(2), one F(4), and one F(6) atom. The Li(3)-O(4) bond length is 2.39 Å. The Li(3)-F(1) bond length is 2.17 Å. The Li(3)-F(2) bond length is 2.05 Å. The Li(3)-F(4) bond length is 1.89 Å. The Li(3)-F(6) bond length is 1.85 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(5), one F(3), one F(5), one F(7), and one F(8) atom. The Li(4)-O(5) bond length is 2.42 Å. The Li(4)-F(3) bond length is 1.98 Å. The Li(4)-F(5) bond length is 2.02 Å. The Li(4)-F(7) bond length is 2.33 Å. The Li(4)-F(8) bond length is 2.03 Å. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(6), one F(4), one F(6), one F(7), and one F(8) atom. The Li(5)-O(6) bond length is 2.37 Å. The Li(5)-F(4) bond length is 1.86 Å. The Li(5)-F(6) bond length is 1.90 Å. The Li(5)-F(7) bond length is 2.21 Å. The Li(5)-F(8) bond length is 2.04 Å. In the sixth Li site, Li(6) is bonded to one O(1), one O(3), one O(6), one O(7), one O(8), and one F(7) atom to form distorted LiO5F octahedra that share corners with two equivalent V(4)O4F2 octahedra,  an edgeedge with one V(2)O4F2 octahedra, edges with two equivalent V(3)O4F2 octahedra, and  a faceface with one V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Li(6)-O(1) bond length is 2.05 Å. The Li(6)-O(3) bond length is 2.14 Å. The Li(6)-O(6) bond length is 2.04 Å. The Li(6)-O(7) bond length is 2.14 Å. The Li(6)-O(8) bond length is 2.01 Å. The Li(6)-F(7) bond length is 1.94 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(7), one F(1), and one F(3) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, and  a faceface with one Li(6)O5F octahedra. The corner-sharing octahedral tilt angles range from 30-44°. The V(1)-O(1) bond length is 1.99 Å. The V(1)-O(3) bond length is 2.17 Å. The V(1)-O(4) bond length is 1.72 Å. The V(1)-O(7) bond length is 1.99 Å. The V(1)-F(1) bond length is 1.97 Å. The V(1)-F(3) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(8), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, and  an edgeedge with one Li(6)O5F octahedra. The corner-sharing octahedral tilt angles range from 35-44°. The V(2)-O(2) bond length is 1.97 Å. The V(2)-O(3) bond length is 1.73 Å. The V(2)-O(4) bond length is 2.21 Å. The V(2)-O(8) bond length is 1.94 Å. The V(2)-F(2) bond length is 1.96 Å. The V(2)-F(4) bond length is 1.96 Å. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one O(7), one F(5), and one F(7) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, and edges with two equivalent Li(6)O5F octahedra. The corner-sharing octahedral tilt angles range from 30-45°. The V(3)-O(1) bond length is 1.80 Å. The V(3)-O(5) bond length is 2.21 Å. The V(3)-O(6) bond length is 1.71 Å. The V(3)-O(7) bond length is 1.79 Å. The V(3)-F(5) bond length is 1.97 Å. The V(3)-F(7) bond length is 2.02 Å. In the fourth V site, V(4) is bonded to one O(2), one O(5), one O(6), one O(8), one F(6), and one F(8) atom to form distorted VO4F2 octahedra that share corners with two equivalent Li(6)O5F octahedra, corners with two equivalent V(2)O4F2 octahedra, and corners with two equivalent V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-60°. The V(4)-O(2) bond length is 1.78 Å. The V(4)-O(5) bond length is 1.72 Å. The V(4)-O(6) bond length is 2.22 Å. The V(4)-O(8) bond length is 1.79 Å. The V(4)-F(6) bond length is 2.00 Å. The V(4)-F(8) bond length is 2.00 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted square co-planar geometry to one Li(1), one Li(6), one V(1), and one V(3) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(6), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(5), one Li(6), one V(3), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(6), one V(1), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(6), one V(2), and one V(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(2), one Li(4), and one V(3) 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(4) atom. In the seventh F site, F(7) is bonded in a distorted tetrahedral geometry to one Li(4), one Li(5), one Li(6), and one V(3) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(4), one Li(5), and one V(4) atom.