Li3V2(O2F)2 crystallizes in the triclinic P1 space group. There are twelve inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), and one F(8) atom to form distorted edge-sharing LiF6 octahedra. In the second Li site, Li(2) 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 distorted edge-sharing LiF6 octahedra. In the third Li site, Li(3) is bonded in a trigonal non-coplanar geometry to one O(3), one F(2), one F(4), and one F(6) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(13), one O(16), one O(4), one O(8), and one O(9) atom to form LiO6 octahedra that share corners with three equivalent V(4)O6 octahedra, corners with three equivalent V(8)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra, edges with two equivalent Li(12)O6 octahedra, and edges with two equivalent Li(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the fifth Li site, Li(5) is bonded in a trigonal non-coplanar geometry to one F(1), one F(3), and one F(5) atom. In the sixth Li site, Li(6) is bonded to one F(2), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form edge-sharing LiF6 octahedra. In the seventh Li site, Li(7) is bonded in a trigonal non-coplanar geometry to one F(1), one F(3), and one F(7) atom. In the eighth Li site, Li(8) is bonded in a distorted trigonal non-coplanar geometry to one O(3), one F(2), one F(6), and one F(8) atom. In the ninth Li site, Li(9) is bonded to one O(1), one O(12), one O(16), one O(5), one O(8), and one O(9) atom to form LiO6 octahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(5)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra,  an edgeedge with one V(8)O6 octahedra, edges with two equivalent Li(12)O6 octahedra, and edges with two equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the tenth Li site, Li(10) is bonded in a 3-coordinate geometry to one O(15), one F(1), one F(5), and one F(7) atom. In the eleventh Li site, Li(11) is bonded in a distorted trigonal non-coplanar geometry to one O(3), one F(4), one F(6), and one F(8) atom. In the twelfth Li site, Li(12) is bonded to one O(1), one O(12), one O(13), one O(16), one O(4), and one O(5) atom to form LiO6 octahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra,  an edgeedge with one V(8)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with two equivalent Li(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(14), one O(3), one O(5), one O(6), and one O(9) atom to form VO6 octahedra that share corners with three equivalent Li(9)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second V site, V(2) is bonded to one O(1), one O(11), one O(13), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share corners with three equivalent Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. In the third V site, V(3) is bonded to one O(10), one O(12), one O(16), one O(2), one O(4), and one O(7) atom to form VO6 octahedra that share corners with three equivalent Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(7)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-13°. In the fourth V site, V(4) is bonded to one O(1), one O(11), one O(13), one O(14), one O(6), and one O(9) atom to form VO6 octahedra that share corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. In the fifth V site, V(5) is bonded to one O(12), one O(15), one O(16), one O(2), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(9)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(7)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the sixth V site, V(6) is bonded to one O(11), one O(13), one O(14), one O(3), one O(5), and one O(9) atom to form VO6 octahedra that share  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the seventh V site, V(7) is bonded to one O(10), one O(12), one O(15), one O(2), one O(4), and one O(8) atom to form VO6 octahedra that share  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. In the eighth V site, V(8) is bonded to one O(10), one O(15), one O(16), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Li(12), one Li(4), one Li(9), one V(1), one V(2), and one V(4) atom to form OLi3V3 octahedra that share corners with three equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(12)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid,  an edgeedge with one O(8)Li2V3 square pyramid, edges with two equivalent O(13)Li2V3 square pyramids, edges with two equivalent O(5)Li2V3 square pyramids, and edges with two equivalent O(9)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(3), one V(5), and one V(7) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(11), one Li(3), one Li(8), one V(1), one V(2), and one V(6) atom. In the fourth O site, O(4) is bonded to one Li(12), one Li(4), one V(3), one V(7), and one V(8) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(13)Li2V3 square pyramids,  an edgeedge with one O(1)Li3V3 octahedra, edges with two equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(12)Li2V3 square pyramid, and  an edgeedge with one O(8)Li2V3 square pyramid. In the fifth O site, O(5) is bonded to one Li(12), one Li(9), one V(1), one V(2), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(12)Li2V3 square pyramids,  an edgeedge with one O(16)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(13)Li2V3 square pyramid, and  an edgeedge with one O(9)Li2V3 square pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(3), one V(5), and one V(8) atom. In the eighth O site, O(8) is bonded to one Li(4), one Li(9), one V(5), one V(7), and one V(8) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid, corners with two equivalent O(9)Li2V3 square pyramids,  an edgeedge with one O(1)Li3V3 octahedra, edges with two equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(12)Li2V3 square pyramid, and  an edgeedge with one O(4)Li2V3 square pyramid. In the ninth O site, O(9) is bonded to one Li(4), one Li(9), one V(1), one V(4), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid, corners with two equivalent O(8)Li2V3 square pyramids,  an edgeedge with one O(16)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(13)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(4), and one V(6) atom. In the twelfth O site, O(12) is bonded to one Li(12), one Li(9), one V(3), one V(5), and one V(7) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(5)Li2V3 square pyramids,  an edgeedge with one O(1)Li3V3 octahedra, edges with two equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(4)Li2V3 square pyramid, and  an edgeedge with one O(8)Li2V3 square pyramid. In the thirteenth O site, O(13) is bonded to one Li(12), one Li(4), one V(2), one V(4), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(4)Li2V3 square pyramids,  an edgeedge with one O(16)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(5)Li2V3 square pyramid, and  an edgeedge with one O(9)Li2V3 square pyramid. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(10), one V(5), one V(7), and one V(8) atom. In the sixteenth O site, O(16) is bonded to one Li(12), one Li(4), one Li(9), one V(3), one V(5), and one V(8) atom to form OLi3V3 octahedra that share corners with three equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(13)Li2V3 square pyramid,  an edgeedge with one O(5)Li2V3 square pyramid,  an edgeedge with one O(9)Li2V3 square pyramid, edges with two equivalent O(12)Li2V3 square pyramids, edges with two equivalent O(4)Li2V3 square pyramids, and edges with two equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(10), one Li(2), one Li(5), and one Li(7) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(6), and one Li(8) atom. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), and one Li(7) atom to form corner-sharing FLi5 square pyramids. The corner-sharing octahedral tilt angles range from 6-13°. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(11), one Li(3), and one Li(6) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(10), one Li(5), and one Li(6) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(11), one Li(2), one Li(3), one Li(6), and one Li(8) atom to form distorted corner-sharing FLi6 octahedra. In the seventh F site, F(7) is bonded in a rectangular see-saw-like geometry to one Li(10), one Li(2), one Li(6), and one Li(7) atom. In the eighth F site, F(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(11), one Li(2), and one Li(8) atom.
Li3V2(O2F)2 crystallizes in the triclinic P1 space group. There are twelve inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), and one F(8) atom to form distorted edge-sharing LiF6 octahedra. The Li(1)-F(1) bond length is 2.30 Å. The Li(1)-F(3) bond length is 2.03 Å. The Li(1)-F(4) bond length is 2.13 Å. The Li(1)-F(5) bond length is 1.96 Å. The Li(1)-F(6) bond length is 2.35 Å. The Li(1)-F(8) bond length is 1.99 Å. In the second Li site, Li(2) 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 distorted edge-sharing LiF6 octahedra. The Li(2)-F(1) bond length is 2.40 Å. The Li(2)-F(2) bond length is 2.14 Å. The Li(2)-F(3) bond length is 1.99 Å. The Li(2)-F(6) bond length is 2.32 Å. The Li(2)-F(7) bond length is 1.97 Å. The Li(2)-F(8) bond length is 1.98 Å. In the third Li site, Li(3) is bonded in a trigonal non-coplanar geometry to one O(3), one F(2), one F(4), and one F(6) atom. The Li(3)-O(3) bond length is 2.62 Å. The Li(3)-F(2) bond length is 1.83 Å. The Li(3)-F(4) bond length is 1.83 Å. The Li(3)-F(6) bond length is 1.91 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(13), one O(16), one O(4), one O(8), and one O(9) atom to form LiO6 octahedra that share corners with three equivalent V(4)O6 octahedra, corners with three equivalent V(8)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra, edges with two equivalent Li(12)O6 octahedra, and edges with two equivalent Li(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. The Li(4)-O(1) bond length is 2.09 Å. The Li(4)-O(13) bond length is 2.15 Å. The Li(4)-O(16) bond length is 2.17 Å. The Li(4)-O(4) bond length is 2.26 Å. The Li(4)-O(8) bond length is 2.15 Å. The Li(4)-O(9) bond length is 2.17 Å. In the fifth Li site, Li(5) is bonded in a trigonal non-coplanar geometry to one F(1), one F(3), and one F(5) atom. The Li(5)-F(1) bond length is 1.82 Å. The Li(5)-F(3) bond length is 1.92 Å. The Li(5)-F(5) bond length is 1.79 Å. In the sixth Li site, Li(6) is bonded to one F(2), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form edge-sharing LiF6 octahedra. The Li(6)-F(2) bond length is 2.00 Å. The Li(6)-F(3) bond length is 1.98 Å. The Li(6)-F(4) bond length is 2.01 Å. The Li(6)-F(5) bond length is 2.16 Å. The Li(6)-F(6) bond length is 2.11 Å. The Li(6)-F(7) bond length is 2.09 Å. In the seventh Li site, Li(7) is bonded in a trigonal non-coplanar geometry to one F(1), one F(3), and one F(7) atom. The Li(7)-F(1) bond length is 1.84 Å. The Li(7)-F(3) bond length is 1.91 Å. The Li(7)-F(7) bond length is 1.83 Å. In the eighth Li site, Li(8) is bonded in a distorted trigonal non-coplanar geometry to one O(3), one F(2), one F(6), and one F(8) atom. The Li(8)-O(3) bond length is 2.57 Å. The Li(8)-F(2) bond length is 1.84 Å. The Li(8)-F(6) bond length is 1.92 Å. The Li(8)-F(8) bond length is 1.85 Å. In the ninth Li site, Li(9) is bonded to one O(1), one O(12), one O(16), one O(5), one O(8), and one O(9) atom to form LiO6 octahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(5)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra,  an edgeedge with one V(8)O6 octahedra, edges with two equivalent Li(12)O6 octahedra, and edges with two equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. The Li(9)-O(1) bond length is 2.13 Å. The Li(9)-O(12) bond length is 2.32 Å. The Li(9)-O(16) bond length is 2.24 Å. The Li(9)-O(5) bond length is 2.17 Å. The Li(9)-O(8) bond length is 2.17 Å. The Li(9)-O(9) bond length is 2.33 Å. In the tenth Li site, Li(10) is bonded in a 3-coordinate geometry to one O(15), one F(1), one F(5), and one F(7) atom. The Li(10)-O(15) bond length is 2.54 Å. The Li(10)-F(1) bond length is 1.83 Å. The Li(10)-F(5) bond length is 1.82 Å. The Li(10)-F(7) bond length is 1.83 Å. In the eleventh Li site, Li(11) is bonded in a distorted trigonal non-coplanar geometry to one O(3), one F(4), one F(6), and one F(8) atom. The Li(11)-O(3) bond length is 2.59 Å. The Li(11)-F(4) bond length is 1.83 Å. The Li(11)-F(6) bond length is 1.92 Å. The Li(11)-F(8) bond length is 1.84 Å. In the twelfth Li site, Li(12) is bonded to one O(1), one O(12), one O(13), one O(16), one O(4), and one O(5) atom to form LiO6 octahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra,  an edgeedge with one V(8)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with two equivalent Li(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. The Li(12)-O(1) bond length is 2.20 Å. The Li(12)-O(12) bond length is 2.12 Å. The Li(12)-O(13) bond length is 2.33 Å. The Li(12)-O(16) bond length is 2.15 Å. The Li(12)-O(4) bond length is 2.12 Å. The Li(12)-O(5) bond length is 2.23 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(14), one O(3), one O(5), one O(6), and one O(9) atom to form VO6 octahedra that share corners with three equivalent Li(9)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. The V(1)-O(1) bond length is 2.09 Å. The V(1)-O(14) bond length is 1.88 Å. The V(1)-O(3) bond length is 2.01 Å. The V(1)-O(5) bond length is 2.04 Å. The V(1)-O(6) bond length is 1.95 Å. The V(1)-O(9) bond length is 1.99 Å. In the second V site, V(2) is bonded to one O(1), one O(11), one O(13), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share corners with three equivalent Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. The V(2)-O(1) bond length is 2.10 Å. The V(2)-O(11) bond length is 1.88 Å. The V(2)-O(13) bond length is 1.98 Å. The V(2)-O(3) bond length is 2.01 Å. The V(2)-O(5) bond length is 2.03 Å. The V(2)-O(6) bond length is 1.95 Å. In the third V site, V(3) is bonded to one O(10), one O(12), one O(16), one O(2), one O(4), and one O(7) atom to form VO6 octahedra that share corners with three equivalent Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(7)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-13°. The V(3)-O(10) bond length is 2.03 Å. The V(3)-O(12) bond length is 2.04 Å. The V(3)-O(16) bond length is 2.08 Å. The V(3)-O(2) bond length is 2.02 Å. The V(3)-O(4) bond length is 2.03 Å. The V(3)-O(7) bond length is 2.05 Å. In the fourth V site, V(4) is bonded to one O(1), one O(11), one O(13), one O(14), one O(6), and one O(9) atom to form VO6 octahedra that share corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. The V(4)-O(1) bond length is 2.08 Å. The V(4)-O(11) bond length is 2.02 Å. The V(4)-O(13) bond length is 2.05 Å. The V(4)-O(14) bond length is 2.02 Å. The V(4)-O(6) bond length is 2.05 Å. The V(4)-O(9) bond length is 2.04 Å. In the fifth V site, V(5) is bonded to one O(12), one O(15), one O(16), one O(2), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(9)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(7)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. The V(5)-O(12) bond length is 2.05 Å. The V(5)-O(15) bond length is 1.99 Å. The V(5)-O(16) bond length is 2.09 Å. The V(5)-O(2) bond length is 1.96 Å. The V(5)-O(7) bond length is 1.84 Å. The V(5)-O(8) bond length is 2.05 Å. In the sixth V site, V(6) is bonded to one O(11), one O(13), one O(14), one O(3), one O(5), and one O(9) atom to form VO6 octahedra that share  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The V(6)-O(11) bond length is 2.01 Å. The V(6)-O(13) bond length is 2.05 Å. The V(6)-O(14) bond length is 2.02 Å. The V(6)-O(3) bond length is 2.03 Å. The V(6)-O(5) bond length is 2.07 Å. The V(6)-O(9) bond length is 2.07 Å. In the seventh V site, V(7) is bonded to one O(10), one O(12), one O(15), one O(2), one O(4), and one O(8) atom to form VO6 octahedra that share  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The V(7)-O(10) bond length is 1.86 Å. The V(7)-O(12) bond length is 2.03 Å. The V(7)-O(15) bond length is 2.00 Å. The V(7)-O(2) bond length is 1.97 Å. The V(7)-O(4) bond length is 2.00 Å. The V(7)-O(8) bond length is 2.02 Å. In the eighth V site, V(8) is bonded to one O(10), one O(15), one O(16), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(12)O6 octahedra,  an edgeedge with one Li(9)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. The V(8)-O(10) bond length is 2.05 Å. The V(8)-O(15) bond length is 2.03 Å. The V(8)-O(16) bond length is 2.06 Å. The V(8)-O(4) bond length is 2.07 Å. The V(8)-O(7) bond length is 2.03 Å. The V(8)-O(8) bond length is 2.07 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Li(12), one Li(4), one Li(9), one V(1), one V(2), and one V(4) atom to form OLi3V3 octahedra that share corners with three equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(12)Li2V3 square pyramid,  an edgeedge with one O(4)Li2V3 square pyramid,  an edgeedge with one O(8)Li2V3 square pyramid, edges with two equivalent O(13)Li2V3 square pyramids, edges with two equivalent O(5)Li2V3 square pyramids, and edges with two equivalent O(9)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(3), one V(5), and one V(7) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(11), one Li(3), one Li(8), one V(1), one V(2), and one V(6) atom. In the fourth O site, O(4) is bonded to one Li(12), one Li(4), one V(3), one V(7), and one V(8) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(13)Li2V3 square pyramids,  an edgeedge with one O(1)Li3V3 octahedra, edges with two equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(12)Li2V3 square pyramid, and  an edgeedge with one O(8)Li2V3 square pyramid. In the fifth O site, O(5) is bonded to one Li(12), one Li(9), one V(1), one V(2), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(12)Li2V3 square pyramids,  an edgeedge with one O(16)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(13)Li2V3 square pyramid, and  an edgeedge with one O(9)Li2V3 square pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(3), one V(5), and one V(8) atom. In the eighth O site, O(8) is bonded to one Li(4), one Li(9), one V(5), one V(7), and one V(8) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid, corners with two equivalent O(9)Li2V3 square pyramids,  an edgeedge with one O(1)Li3V3 octahedra, edges with two equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(12)Li2V3 square pyramid, and  an edgeedge with one O(4)Li2V3 square pyramid. In the ninth O site, O(9) is bonded to one Li(4), one Li(9), one V(1), one V(4), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid, corners with two equivalent O(8)Li2V3 square pyramids,  an edgeedge with one O(16)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(13)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(4), and one V(6) atom. In the twelfth O site, O(12) is bonded to one Li(12), one Li(9), one V(3), one V(5), and one V(7) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(13)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(5)Li2V3 square pyramids,  an edgeedge with one O(1)Li3V3 octahedra, edges with two equivalent O(16)Li3V3 octahedra,  an edgeedge with one O(4)Li2V3 square pyramid, and  an edgeedge with one O(8)Li2V3 square pyramid. In the thirteenth O site, O(13) is bonded to one Li(12), one Li(4), one V(2), one V(4), and one V(6) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(12)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(8)Li2V3 square pyramid,  a cornercorner with one O(9)Li2V3 square pyramid, corners with two equivalent O(4)Li2V3 square pyramids,  an edgeedge with one O(16)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(5)Li2V3 square pyramid, and  an edgeedge with one O(9)Li2V3 square pyramid. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(10), one V(5), one V(7), and one V(8) atom. In the sixteenth O site, O(16) is bonded to one Li(12), one Li(4), one Li(9), one V(3), one V(5), and one V(8) atom to form OLi3V3 octahedra that share corners with three equivalent O(1)Li3V3 octahedra,  an edgeedge with one O(13)Li2V3 square pyramid,  an edgeedge with one O(5)Li2V3 square pyramid,  an edgeedge with one O(9)Li2V3 square pyramid, edges with two equivalent O(12)Li2V3 square pyramids, edges with two equivalent O(4)Li2V3 square pyramids, and edges with two equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(10), one Li(2), one Li(5), and one Li(7) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(6), and one Li(8) atom. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), and one Li(7) atom to form corner-sharing FLi5 square pyramids. The corner-sharing octahedral tilt angles range from 6-13°. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(11), one Li(3), and one Li(6) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(10), one Li(5), and one Li(6) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(11), one Li(2), one Li(3), one Li(6), and one Li(8) atom to form distorted corner-sharing FLi6 octahedra. In the seventh F site, F(7) is bonded in a rectangular see-saw-like geometry to one Li(10), one Li(2), one Li(6), and one Li(7) atom. In the eighth F site, F(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(11), one Li(2), and one Li(8) atom.