Li2VOF3 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(11), one F(3), and one F(5) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(3)O2F4 octahedra, corners with two equivalent V(2)O2F4 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(4)F4 tetrahedra, and  an edgeedge with one V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 51-75°. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one F(12), one F(2), one F(4), and one F(6) atom. In the third Li site, Li(3) is bonded to one F(10), one F(2), one F(3), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(2)O2F4 octahedra, corners with two equivalent V(1)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and  an edgeedge with one V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-76°. In the fourth Li site, Li(4) is bonded to one F(1), one F(4), one F(8), and one F(9) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(4)O2F4 octahedra, corners with two equivalent V(3)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and  an edgeedge with one V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-75°. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(1), one O(4), one F(1), one F(5), and one F(7) atom. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(2), one O(3), one F(2), one F(6), and one F(8) atom. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one O(1), one O(3), one F(3), one F(6), and one F(7) atom. In the eighth Li site, Li(8) is bonded in a 5-coordinate geometry to one O(2), one O(4), one F(4), one F(5), and one F(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one F(10), one F(11), one F(3), and one F(6) atom to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra, corners with two equivalent V(4)O2F4 octahedra, corners with two equivalent Li(3)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-46°. In the second V site, V(2) is bonded to one O(1), one O(3), one F(1), one F(11), one F(7), and one F(9) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra, corners with two equivalent V(3)O2F4 octahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-46°. In the third V site, V(3) is bonded to one O(1), one O(4), one F(12), one F(4), one F(5), and one F(9) atom to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra, corners with two equivalent V(4)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and corners with two equivalent Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-44°. In the fourth V site, V(4) is bonded to one O(2), one O(4), one F(10), one F(12), one F(2), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra, corners with two equivalent V(3)O2F4 octahedra,  a cornercorner with one Li(4)F4 tetrahedra, and  an edgeedge with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-44°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(7), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(6), one Li(8), one V(1), and one V(4) atom. In the third O site, O(3) is bonded to one Li(6), one Li(7), one V(1), and one V(2) atom to form distorted OLi2V2 trigonal pyramids that share  a cornercorner with one F(6)Li3V tetrahedra,  a cornercorner with one F(8)Li3V tetrahedra, corners with two equivalent F(7)Li3V tetrahedra, and  an edgeedge with one F(6)Li3V tetrahedra. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(8), one V(3), and one V(4) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one Li(5), and one V(2) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Li(6), and one V(4) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Li(7), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(4), one Li(8), and one V(3) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(5), one Li(8), and one V(3) atom to form distorted corner-sharing FLi3V tetrahedra. In the sixth F site, F(6) is bonded to one Li(2), one Li(6), one Li(7), and one V(1) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one F(7)Li3V tetrahedra,  a cornercorner with one F(8)Li3V tetrahedra,  a cornercorner with one O(3)Li2V2 trigonal pyramid, and  an edgeedge with one O(3)Li2V2 trigonal pyramid. In the seventh F site, F(7) is bonded to one Li(3), one Li(5), one Li(7), and one V(2) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one F(5)Li3V tetrahedra,  a cornercorner with one F(6)Li3V tetrahedra, and corners with two equivalent O(3)Li2V2 trigonal pyramids. In the eighth F site, F(8) is bonded to one Li(4), one Li(6), one Li(8), and one V(4) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one F(5)Li3V tetrahedra,  a cornercorner with one F(6)Li3V tetrahedra, and  a cornercorner with one O(3)Li2V2 trigonal pyramid. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(4), one V(2), and one V(3) atom. In the tenth F site, F(10) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(4) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one V(2) atom. In the twelfth F site, F(12) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one V(4) atom.
Li2VOF3 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(11), one F(3), and one F(5) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(3)O2F4 octahedra, corners with two equivalent V(2)O2F4 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(4)F4 tetrahedra, and  an edgeedge with one V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 51-75°. The Li(1)-F(1) bond length is 1.92 Å. The Li(1)-F(11) bond length is 1.97 Å. The Li(1)-F(3) bond length is 2.01 Å. The Li(1)-F(5) bond length is 1.90 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one F(12), one F(2), one F(4), and one F(6) atom. The Li(2)-F(12) bond length is 1.93 Å. The Li(2)-F(2) bond length is 1.91 Å. The Li(2)-F(4) bond length is 2.03 Å. The Li(2)-F(6) bond length is 1.90 Å. In the third Li site, Li(3) is bonded to one F(10), one F(2), one F(3), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(2)O2F4 octahedra, corners with two equivalent V(1)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and  an edgeedge with one V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-76°. The Li(3)-F(10) bond length is 1.95 Å. The Li(3)-F(2) bond length is 2.08 Å. The Li(3)-F(3) bond length is 1.92 Å. The Li(3)-F(7) bond length is 1.90 Å. In the fourth Li site, Li(4) is bonded to one F(1), one F(4), one F(8), and one F(9) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(4)O2F4 octahedra, corners with two equivalent V(3)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and  an edgeedge with one V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-75°. The Li(4)-F(1) bond length is 2.03 Å. The Li(4)-F(4) bond length is 1.93 Å. The Li(4)-F(8) bond length is 1.92 Å. The Li(4)-F(9) bond length is 1.96 Å. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(1), one O(4), one F(1), one F(5), and one F(7) atom. The Li(5)-O(1) bond length is 2.04 Å. The Li(5)-O(4) bond length is 2.08 Å. The Li(5)-F(1) bond length is 1.96 Å. The Li(5)-F(5) bond length is 1.93 Å. The Li(5)-F(7) bond length is 2.26 Å. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(2), one O(3), one F(2), one F(6), and one F(8) atom. The Li(6)-O(2) bond length is 2.13 Å. The Li(6)-O(3) bond length is 2.02 Å. The Li(6)-F(2) bond length is 1.96 Å. The Li(6)-F(6) bond length is 1.92 Å. The Li(6)-F(8) bond length is 2.30 Å. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one O(1), one O(3), one F(3), one F(6), and one F(7) atom. The Li(7)-O(1) bond length is 2.07 Å. The Li(7)-O(3) bond length is 2.03 Å. The Li(7)-F(3) bond length is 1.96 Å. The Li(7)-F(6) bond length is 2.29 Å. The Li(7)-F(7) bond length is 1.93 Å. In the eighth Li site, Li(8) is bonded in a 5-coordinate geometry to one O(2), one O(4), one F(4), one F(5), and one F(8) atom. The Li(8)-O(2) bond length is 2.33 Å. The Li(8)-O(4) bond length is 2.01 Å. The Li(8)-F(4) bond length is 1.94 Å. The Li(8)-F(5) bond length is 2.14 Å. The Li(8)-F(8) bond length is 1.94 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one F(10), one F(11), one F(3), and one F(6) atom to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra, corners with two equivalent V(4)O2F4 octahedra, corners with two equivalent Li(3)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-46°. The V(1)-O(2) bond length is 1.84 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-F(10) bond length is 2.09 Å. The V(1)-F(11) bond length is 2.12 Å. The V(1)-F(3) bond length is 2.05 Å. The V(1)-F(6) bond length is 2.05 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one F(1), one F(11), one F(7), and one F(9) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra, corners with two equivalent V(3)O2F4 octahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-46°. The V(2)-O(1) bond length is 1.94 Å. The V(2)-O(3) bond length is 1.89 Å. The V(2)-F(1) bond length is 2.06 Å. The V(2)-F(11) bond length is 2.09 Å. The V(2)-F(7) bond length is 2.08 Å. The V(2)-F(9) bond length is 2.14 Å. In the third V site, V(3) is bonded to one O(1), one O(4), one F(12), one F(4), one F(5), and one F(9) atom to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra, corners with two equivalent V(4)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and corners with two equivalent Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-44°. The V(3)-O(1) bond length is 1.89 Å. The V(3)-O(4) bond length is 1.93 Å. The V(3)-F(12) bond length is 2.13 Å. The V(3)-F(4) bond length is 2.08 Å. The V(3)-F(5) bond length is 2.09 Å. The V(3)-F(9) bond length is 2.09 Å. In the fourth V site, V(4) is bonded to one O(2), one O(4), one F(10), one F(12), one F(2), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra, corners with two equivalent V(3)O2F4 octahedra,  a cornercorner with one Li(4)F4 tetrahedra, and  an edgeedge with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-44°. The V(4)-O(2) bond length is 1.85 Å. The V(4)-O(4) bond length is 1.93 Å. The V(4)-F(10) bond length is 2.13 Å. The V(4)-F(12) bond length is 2.09 Å. The V(4)-F(2) bond length is 2.05 Å. The V(4)-F(8) bond length is 2.06 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(7), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(6), one Li(8), one V(1), and one V(4) atom. In the third O site, O(3) is bonded to one Li(6), one Li(7), one V(1), and one V(2) atom to form distorted OLi2V2 trigonal pyramids that share  a cornercorner with one F(6)Li3V tetrahedra,  a cornercorner with one F(8)Li3V tetrahedra, corners with two equivalent F(7)Li3V tetrahedra, and  an edgeedge with one F(6)Li3V tetrahedra. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(8), one V(3), and one V(4) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one Li(5), and one V(2) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Li(6), and one V(4) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Li(7), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(4), one Li(8), and one V(3) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(5), one Li(8), and one V(3) atom to form distorted corner-sharing FLi3V tetrahedra. In the sixth F site, F(6) is bonded to one Li(2), one Li(6), one Li(7), and one V(1) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one F(7)Li3V tetrahedra,  a cornercorner with one F(8)Li3V tetrahedra,  a cornercorner with one O(3)Li2V2 trigonal pyramid, and  an edgeedge with one O(3)Li2V2 trigonal pyramid. In the seventh F site, F(7) is bonded to one Li(3), one Li(5), one Li(7), and one V(2) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one F(5)Li3V tetrahedra,  a cornercorner with one F(6)Li3V tetrahedra, and corners with two equivalent O(3)Li2V2 trigonal pyramids. In the eighth F site, F(8) is bonded to one Li(4), one Li(6), one Li(8), and one V(4) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one F(5)Li3V tetrahedra,  a cornercorner with one F(6)Li3V tetrahedra, and  a cornercorner with one O(3)Li2V2 trigonal pyramid. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(4), one V(2), and one V(3) atom. In the tenth F site, F(10) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(4) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one V(2) atom. In the twelfth F site, F(12) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one V(4) atom.