Li2VO2F is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(5), one O(6), one F(1), one F(3), and one F(4) atom to form LiO3F3 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent V(4)O5F octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Li(7)O4F2 octahedra, and edges with two equivalent Li(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Li site, Li(2) is bonded to one O(2), one O(7), one O(8), one F(1), one F(3), and one F(4) atom to form LiO3F3 octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(4)O5F octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, and edges with two equivalent Li(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third Li site, Li(3) is bonded to one O(4), one O(7), one O(8), one F(2), one F(3), and one F(4) atom to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(4)O4F2 octahedra,  a cornercorner with one V(4)O5F octahedra, corners with two equivalent Li(1)O3F3 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, and edges with two equivalent Li(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the fourth Li site, Li(4) is bonded to one O(3), one O(4), one O(5), one O(6), one F(3), and one F(4) atom to form distorted LiO4F2 octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one V(4)O5F octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(7)O4F2 octahedra, and edges with two equivalent Li(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(7), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(7)O4F2 octahedra,  a cornercorner with one V(1)O5F octahedra, corners with two equivalent Li(8)O4F2 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, and edges with two equivalent Li(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the sixth Li site, Li(6) is bonded to one O(2), one O(4), one O(8), one F(1), one F(2), and one F(4) atom to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(8)O4F2 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with two equivalent Li(7)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, and edges with two equivalent Li(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the seventh Li site, Li(7) is bonded to one O(1), one O(3), one O(4), one O(5), one F(1), and one F(3) atom to form distorted LiO4F2 octahedra that share  a cornercorner with one Li(5)O3F3 octahedra,  a cornercorner with one V(1)O5F octahedra, corners with two equivalent Li(6)O3F3 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the eighth Li site, Li(8) is bonded to one O(1), one O(3), one O(4), one O(6), one F(1), and one F(4) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(6)O3F3 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with two equivalent Li(5)O3F3 octahedra, corners with two equivalent V(1)O5F octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(7), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(5)O3F3 octahedra,  a cornercorner with one Li(7)O4F2 octahedra, corners with two equivalent Li(6)O3F3 octahedra, corners with two equivalent Li(8)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(8), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(6)O3F3 octahedra,  a cornercorner with one Li(8)O4F2 octahedra, corners with two equivalent Li(5)O3F3 octahedra, corners with two equivalent Li(7)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Li(2)O3F3 octahedra, corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(6), one O(7), one O(8), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra, corners with two equivalent Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(7), one Li(8), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(4)Li6 octahedra, corners with two equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second O site, O(2) is bonded to one Li(2), one Li(5), one Li(6), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent O(8)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the third O site, O(3) is bonded to one Li(4), one Li(7), one Li(8), one V(1), one V(2), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li6 octahedra,  a cornercorner with one F(2)Li3V3 octahedra, corners with two equivalent O(2)Li3V3 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one Li(8) atom to form OLi6 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one F(2)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, edges with two equivalent F(3)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one Li(7), one V(1), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(7)Li3V3 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with two equivalent O(8)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the sixth O site, O(6) is bonded to one Li(1), one Li(4), one Li(8), one V(2), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(8)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(7)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(5)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(5), one V(1), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with two equivalent O(6)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(8)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-18°. In the eighth O site, O(8) is bonded to one Li(2), one Li(3), one Li(6), one V(2), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-18°. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), one Li(7), and one Li(8) atom to form FLi6 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra, edges with two equivalent O(4)Li6 octahedra, edges with two equivalent F(3)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. In the second F site, F(2) is bonded to one Li(3), one Li(5), one Li(6), one V(1), one V(2), and one V(4) atom to form FLi3V3 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(4)Li6 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent O(8)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(7) atom to form FLi6 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra,  a cornercorner with one O(7)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra, corners with two equivalent O(8)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(4)Li6 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Li(8) atom to form FLi6 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra,  a cornercorner with one O(8)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent O(7)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(4)Li6 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°.
Li2VO2F is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(5), one O(6), one F(1), one F(3), and one F(4) atom to form LiO3F3 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent V(4)O5F octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Li(7)O4F2 octahedra, and edges with two equivalent Li(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Li(1)-O(1) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.30 Å. The Li(1)-O(6) bond length is 2.32 Å. The Li(1)-F(1) bond length is 2.10 Å. The Li(1)-F(3) bond length is 2.02 Å. The Li(1)-F(4) bond length is 2.02 Å. In the second Li site, Li(2) is bonded to one O(2), one O(7), one O(8), one F(1), one F(3), and one F(4) atom to form LiO3F3 octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(4)O5F octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, and edges with two equivalent Li(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The Li(2)-O(2) bond length is 2.19 Å. The Li(2)-O(7) bond length is 2.28 Å. The Li(2)-O(8) bond length is 2.26 Å. The Li(2)-F(1) bond length is 2.11 Å. The Li(2)-F(3) bond length is 2.02 Å. The Li(2)-F(4) bond length is 2.02 Å. In the third Li site, Li(3) is bonded to one O(4), one O(7), one O(8), one F(2), one F(3), and one F(4) atom to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(4)O4F2 octahedra,  a cornercorner with one V(4)O5F octahedra, corners with two equivalent Li(1)O3F3 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, and edges with two equivalent Li(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. The Li(3)-O(4) bond length is 1.87 Å. The Li(3)-O(7) bond length is 2.28 Å. The Li(3)-O(8) bond length is 2.27 Å. The Li(3)-F(2) bond length is 2.42 Å. The Li(3)-F(3) bond length is 2.12 Å. The Li(3)-F(4) bond length is 2.11 Å. In the fourth Li site, Li(4) is bonded to one O(3), one O(4), one O(5), one O(6), one F(3), and one F(4) atom to form distorted LiO4F2 octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one V(4)O5F octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(7)O4F2 octahedra, and edges with two equivalent Li(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. The Li(4)-O(3) bond length is 2.38 Å. The Li(4)-O(4) bond length is 1.90 Å. The Li(4)-O(5) bond length is 2.26 Å. The Li(4)-O(6) bond length is 2.26 Å. The Li(4)-F(3) bond length is 2.13 Å. The Li(4)-F(4) bond length is 2.14 Å. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(7), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(7)O4F2 octahedra,  a cornercorner with one V(1)O5F octahedra, corners with two equivalent Li(8)O4F2 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, and edges with two equivalent Li(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Li(5)-O(2) bond length is 2.46 Å. The Li(5)-O(4) bond length is 1.90 Å. The Li(5)-O(7) bond length is 2.32 Å. The Li(5)-F(1) bond length is 1.98 Å. The Li(5)-F(2) bond length is 2.31 Å. The Li(5)-F(3) bond length is 2.06 Å. In the sixth Li site, Li(6) is bonded to one O(2), one O(4), one O(8), one F(1), one F(2), and one F(4) atom to form distorted LiO3F3 octahedra that share  a cornercorner with one Li(8)O4F2 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with two equivalent Li(7)O4F2 octahedra, corners with two equivalent V(1)O5F octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, and edges with two equivalent Li(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Li(6)-O(2) bond length is 2.48 Å. The Li(6)-O(4) bond length is 1.90 Å. The Li(6)-O(8) bond length is 2.31 Å. The Li(6)-F(1) bond length is 1.98 Å. The Li(6)-F(2) bond length is 2.30 Å. The Li(6)-F(4) bond length is 2.06 Å. In the seventh Li site, Li(7) is bonded to one O(1), one O(3), one O(4), one O(5), one F(1), and one F(3) atom to form distorted LiO4F2 octahedra that share  a cornercorner with one Li(5)O3F3 octahedra,  a cornercorner with one V(1)O5F octahedra, corners with two equivalent Li(6)O3F3 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. The Li(7)-O(1) bond length is 2.35 Å. The Li(7)-O(3) bond length is 2.28 Å. The Li(7)-O(4) bond length is 1.93 Å. The Li(7)-O(5) bond length is 2.28 Å. The Li(7)-F(1) bond length is 2.09 Å. The Li(7)-F(3) bond length is 2.11 Å. In the eighth Li site, Li(8) is bonded to one O(1), one O(3), one O(4), one O(6), one F(1), and one F(4) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(6)O3F3 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with two equivalent Li(5)O3F3 octahedra, corners with two equivalent V(1)O5F octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one V(2)O5F octahedra,  an edgeedge with one V(4)O5F octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent Li(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. The Li(8)-O(1) bond length is 2.33 Å. The Li(8)-O(3) bond length is 2.29 Å. The Li(8)-O(4) bond length is 1.93 Å. The Li(8)-O(6) bond length is 2.29 Å. The Li(8)-F(1) bond length is 2.10 Å. The Li(8)-F(4) bond length is 2.10 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(7), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(5)O3F3 octahedra,  a cornercorner with one Li(7)O4F2 octahedra, corners with two equivalent Li(6)O3F3 octahedra, corners with two equivalent Li(8)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 2.01 Å. The V(1)-O(5) bond length is 2.03 Å. The V(1)-O(7) bond length is 2.05 Å. The V(1)-F(2) bond length is 2.17 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(8), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(6)O3F3 octahedra,  a cornercorner with one Li(8)O4F2 octahedra, corners with two equivalent Li(5)O3F3 octahedra, corners with two equivalent Li(7)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(2) bond length is 2.02 Å. The V(2)-O(3) bond length is 2.01 Å. The V(2)-O(6) bond length is 2.04 Å. The V(2)-O(8) bond length is 2.05 Å. The V(2)-F(2) bond length is 2.17 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Li(2)O3F3 octahedra, corners with two equivalent Li(3)O3F3 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-13°. The V(3)-O(1) bond length is 2.08 Å. The V(3)-O(2) bond length is 2.10 Å. The V(3)-O(5) bond length is 2.05 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-O(7) bond length is 2.05 Å. The V(3)-O(8) bond length is 2.06 Å. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(6), one O(7), one O(8), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(3)O3F3 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra, corners with two equivalent Li(2)O3F3 octahedra,  an edgeedge with one Li(3)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one Li(6)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one Li(7)O4F2 octahedra,  an edgeedge with one Li(8)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. The V(4)-O(3) bond length is 2.04 Å. The V(4)-O(5) bond length is 2.03 Å. The V(4)-O(6) bond length is 2.03 Å. The V(4)-O(7) bond length is 2.03 Å. The V(4)-O(8) bond length is 2.04 Å. The V(4)-F(2) bond length is 2.16 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(7), one Li(8), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(4)Li6 octahedra, corners with two equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second O site, O(2) is bonded to one Li(2), one Li(5), one Li(6), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(4)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent O(8)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the third O site, O(3) is bonded to one Li(4), one Li(7), one Li(8), one V(1), one V(2), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li6 octahedra,  a cornercorner with one F(2)Li3V3 octahedra, corners with two equivalent O(2)Li3V3 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one Li(8) atom to form OLi6 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one F(2)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, edges with two equivalent F(3)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one Li(7), one V(1), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(7)Li3V3 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with two equivalent O(8)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the sixth O site, O(6) is bonded to one Li(1), one Li(4), one Li(8), one V(2), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(8)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(7)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(5)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(5), one V(1), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with two equivalent O(6)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(8)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-18°. In the eighth O site, O(8) is bonded to one Li(2), one Li(3), one Li(6), one V(2), one V(3), and one V(4) atom to form OLi3V3 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-18°. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), one Li(7), and one Li(8) atom to form FLi6 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra, edges with two equivalent O(4)Li6 octahedra, edges with two equivalent F(3)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. In the second F site, F(2) is bonded to one Li(3), one Li(5), one Li(6), one V(1), one V(2), and one V(4) atom to form FLi3V3 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(4)Li6 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent F(1)Li6 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(4)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent O(8)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(7) atom to form FLi6 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra,  a cornercorner with one O(7)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra, corners with two equivalent O(8)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(4)Li6 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Li(8) atom to form FLi6 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra,  a cornercorner with one O(8)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent O(7)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(8)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(4)Li6 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°.