Li2V3(OF)4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(4), and one O(6) atom. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and edges with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the fourth Li site, Li(4) is bonded to one F(1), one F(2), one F(3), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and edges with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(7), one O(8), one F(3), one F(4), and one F(7) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra, and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the third V site, V(3) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the fourth V site, V(4) is bonded to one O(3), one O(7), one O(8), one F(3), one F(4), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra, and edges with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(5), one F(1), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the sixth V site, V(6) is bonded to one O(1), one O(2), one O(6), one F(2), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(2), one V(5), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(5)LiV3 tetrahedra,  a cornercorner with one O(6)LiV3 tetrahedra, edges with two equivalent O(2)Li2V3 square pyramids,  an edgeedge with one O(5)LiV3 tetrahedra, and  an edgeedge with one O(6)LiV3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(3), one V(5), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(5)LiV3 tetrahedra,  a cornercorner with one O(6)LiV3 tetrahedra, edges with two equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(5)LiV3 tetrahedra, and  an edgeedge with one O(6)LiV3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded to one Li(1), one V(2), one V(3), and one V(5) atom to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid, corners with two equivalent O(6)LiV3 tetrahedra,  an edgeedge with one O(1)Li2V3 square pyramid, and  an edgeedge with one O(2)Li2V3 square pyramid. In the sixth O site, O(6) is bonded to one Li(2), one V(2), one V(3), and one V(6) atom to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid, corners with two equivalent O(5)LiV3 tetrahedra,  an edgeedge with one O(1)Li2V3 square pyramid, and  an edgeedge with one O(2)Li2V3 square pyramid. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(6) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one V(4) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(5), and one V(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(4), one V(5), and one V(6) atom. In the seventh F site, F(7) is bonded in a trigonal non-coplanar geometry to one Li(3), one Li(4), and one V(1) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(3), one Li(4), and one V(4) atom.
Li2V3(OF)4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.12 Å. The Li(1)-O(5) bond length is 1.88 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(4), and one O(6) atom. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(2) bond length is 2.02 Å. The Li(2)-O(4) bond length is 2.10 Å. The Li(2)-O(6) bond length is 1.86 Å. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and edges with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Li(3)-F(1) bond length is 2.02 Å. The Li(3)-F(2) bond length is 2.03 Å. The Li(3)-F(4) bond length is 2.27 Å. The Li(3)-F(5) bond length is 2.07 Å. The Li(3)-F(7) bond length is 2.01 Å. The Li(3)-F(8) bond length is 2.08 Å. In the fourth Li site, Li(4) is bonded to one F(1), one F(2), one F(3), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and edges with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Li(4)-F(1) bond length is 2.01 Å. The Li(4)-F(2) bond length is 2.02 Å. The Li(4)-F(3) bond length is 2.20 Å. The Li(4)-F(6) bond length is 2.07 Å. The Li(4)-F(7) bond length is 2.03 Å. The Li(4)-F(8) bond length is 2.10 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(7), one O(8), one F(3), one F(4), and one F(7) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra, and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. The V(1)-O(4) bond length is 2.03 Å. The V(1)-O(7) bond length is 2.05 Å. The V(1)-O(8) bond length is 2.02 Å. The V(1)-F(3) bond length is 2.03 Å. The V(1)-F(4) bond length is 2.05 Å. The V(1)-F(7) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(3) bond length is 2.11 Å. The V(2)-O(4) bond length is 1.90 Å. The V(2)-O(5) bond length is 1.94 Å. The V(2)-O(6) bond length is 1.95 Å. The V(2)-O(7) bond length is 1.96 Å. In the third V site, V(3) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. The V(3)-O(2) bond length is 2.04 Å. The V(3)-O(3) bond length is 2.08 Å. The V(3)-O(4) bond length is 2.08 Å. The V(3)-O(5) bond length is 2.08 Å. The V(3)-O(6) bond length is 2.07 Å. The V(3)-O(8) bond length is 1.98 Å. In the fourth V site, V(4) is bonded to one O(3), one O(7), one O(8), one F(3), one F(4), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Li(4)F6 octahedra, and edges with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. The V(4)-O(3) bond length is 1.85 Å. The V(4)-O(7) bond length is 1.93 Å. The V(4)-O(8) bond length is 1.92 Å. The V(4)-F(3) bond length is 2.03 Å. The V(4)-F(4) bond length is 2.03 Å. The V(4)-F(8) bond length is 1.89 Å. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(5), one F(1), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. The V(5)-O(1) bond length is 2.04 Å. The V(5)-O(2) bond length is 2.07 Å. The V(5)-O(5) bond length is 2.01 Å. The V(5)-F(1) bond length is 1.94 Å. The V(5)-F(5) bond length is 2.05 Å. The V(5)-F(6) bond length is 2.03 Å. In the sixth V site, V(6) is bonded to one O(1), one O(2), one O(6), one F(2), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(4)F6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The V(6)-O(1) bond length is 2.06 Å. The V(6)-O(2) bond length is 2.04 Å. The V(6)-O(6) bond length is 2.02 Å. The V(6)-F(2) bond length is 1.94 Å. The V(6)-F(5) bond length is 2.03 Å. The V(6)-F(6) bond length is 2.05 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(2), one V(5), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(5)LiV3 tetrahedra,  a cornercorner with one O(6)LiV3 tetrahedra, edges with two equivalent O(2)Li2V3 square pyramids,  an edgeedge with one O(5)LiV3 tetrahedra, and  an edgeedge with one O(6)LiV3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(3), one V(5), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(5)LiV3 tetrahedra,  a cornercorner with one O(6)LiV3 tetrahedra, edges with two equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(5)LiV3 tetrahedra, and  an edgeedge with one O(6)LiV3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded to one Li(1), one V(2), one V(3), and one V(5) atom to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid, corners with two equivalent O(6)LiV3 tetrahedra,  an edgeedge with one O(1)Li2V3 square pyramid, and  an edgeedge with one O(2)Li2V3 square pyramid. In the sixth O site, O(6) is bonded to one Li(2), one V(2), one V(3), and one V(6) atom to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid, corners with two equivalent O(5)LiV3 tetrahedra,  an edgeedge with one O(1)Li2V3 square pyramid, and  an edgeedge with one O(2)Li2V3 square pyramid. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one V(6) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one V(4) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(5), and one V(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(4), one V(5), and one V(6) atom. In the seventh F site, F(7) is bonded in a trigonal non-coplanar geometry to one Li(3), one Li(4), and one V(1) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(3), one Li(4), and one V(4) atom.