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), two equivalent O(4), one F(4), and two equivalent F(2) atoms to form LiO3F3 octahedra that share  a cornercorner with one Li(7)O3F3 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(7), one F(2), and two equivalent F(4) atoms to form LiO3F3 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(5)O3F3 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(6), two equivalent O(8), one F(1), and one F(3) atom. In the fourth Li site, Li(4) is bonded to one O(2), one O(8), two equivalent O(5), and two equivalent F(3) atoms to form distorted LiO4F2 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(7)O3F3 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(7)O3F3 octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. In the fifth Li site, Li(5) is bonded to one O(4), two equivalent O(2), one F(3), and two equivalent F(4) atoms to form LiO3F3 octahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent V(4)O4F2 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one V(4)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(7), one O(8), two equivalent F(1), and two equivalent F(2) atoms. In the seventh Li site, Li(7) is bonded to one O(6), two equivalent O(3), one F(4), and two equivalent F(3) atoms to form LiO3F3 octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one V(4)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one O(5), two equivalent O(1), two equivalent O(8), and one F(2) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra,  an edgeedge with one Li(1)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, edges with two equivalent V(4)O4F2 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the second V site, V(2) is bonded to one O(1), two equivalent O(5), two equivalent O(7), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(1)O3F3 octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent V(4)O4F2 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 3-19°. In the third V site, V(3) is bonded to one O(4), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one Li(5)O3F3 octahedra, corners with two equivalent Li(7)O3F3 octahedra,  an edgeedge with one Li(7)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the fourth V site, V(4) is bonded to one O(5), one O(6), two equivalent O(2), and two equivalent F(1) atoms to form VO4F2 octahedra that share  a cornercorner with one Li(7)O3F3 octahedra, corners with two equivalent Li(5)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent V(4)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(8), one V(2), and two equivalent V(3) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one F(1)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(8)Li6 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(8)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Li(4), two equivalent Li(5), one V(1), and two equivalent V(4) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(8)Li6 octahedra, corners with two equivalent F(1)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one F(1)Li3V3 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(7), one V(1), and two equivalent V(3) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(5), two equivalent Li(1), one V(3), and two equivalent V(1) atoms 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(6)Li3V3 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the fifth O site, O(5) is bonded to one Li(8), two equivalent Li(4), one V(4), and two equivalent V(2) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with two equivalent O(7)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, and edges with two equivalent F(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 9-22°. In the sixth O site, O(6) is bonded to one Li(7), two equivalent Li(3), one V(4), and two equivalent V(1) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(8)Li6 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(8)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent F(1)Li3V3 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-17°. In the seventh O site, O(7) is bonded to one Li(6), two equivalent Li(2), one V(3), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(8)Li6 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one O(5)Li3V3 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, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent F(1)Li3V3 octahedra, and edges with two equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 1-16°. In the eighth O site, O(8) is bonded to one Li(4), one Li(6), two equivalent Li(3), and two equivalent Li(8) atoms to form OLi6 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(7)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, edges with two equivalent F(1)Li3V3 octahedra, edges with two equivalent F(2)Li6 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 7-17°. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), two equivalent Li(6), one V(2), and two equivalent V(4) atoms to form FLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with two equivalent O(2)Li3V3 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, and edges with two equivalent F(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-23°. In the second F site, F(2) is bonded to one Li(2), one Li(8), two equivalent Li(1), and two equivalent Li(6) atoms to form FLi6 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(5)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent F(1)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one F(1)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, edges with two equivalent F(2)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-22°. In the third F site, F(3) is bonded to one Li(3), one Li(5), two equivalent Li(4), and two equivalent Li(7) atoms to form FLi6 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one F(1)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(8)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 6-23°. In the fourth F site, F(4) is bonded to one Li(1), one Li(7), two equivalent Li(2), and two equivalent Li(5) atoms to form FLi6 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(6)Li3V3 octahedra, corners with two equivalent O(2)Li3V3 octahedra, corners with two equivalent O(7)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(2)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 4-9°.
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), two equivalent O(4), one F(4), and two equivalent F(2) atoms to form LiO3F3 octahedra that share  a cornercorner with one Li(7)O3F3 octahedra,  a cornercorner with one V(2)O5F octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Li(1)-O(1) bond length is 2.12 Å. There is one shorter (2.25 Å) and one longer (2.28 Å) Li(1)-O(4) bond length. The Li(1)-F(4) bond length is 2.09 Å. Both Li(1)-F(2) bond lengths are 2.07 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(7), one F(2), and two equivalent F(4) atoms to form LiO3F3 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(5)O3F3 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(5)O3F3 octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. The Li(2)-O(3) bond length is 2.16 Å. There is one shorter (2.23 Å) and one longer (2.28 Å) Li(2)-O(7) bond length. The Li(2)-F(2) bond length is 1.98 Å. There is one shorter (2.10 Å) and one longer (2.11 Å) Li(2)-F(4) bond length. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(6), two equivalent O(8), one F(1), and one F(3) atom. There is one shorter (2.51 Å) and one longer (2.55 Å) Li(3)-O(6) bond length. Both Li(3)-O(8) bond lengths are 1.93 Å. The Li(3)-F(1) bond length is 2.26 Å. The Li(3)-F(3) bond length is 2.10 Å. In the fourth Li site, Li(4) is bonded to one O(2), one O(8), two equivalent O(5), and two equivalent F(3) atoms to form distorted LiO4F2 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(7)O3F3 octahedra, corners with two equivalent V(2)O5F octahedra,  an edgeedge with one Li(7)O3F3 octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. The Li(4)-O(2) bond length is 2.32 Å. The Li(4)-O(8) bond length is 1.90 Å. There is one shorter (2.38 Å) and one longer (2.42 Å) Li(4)-O(5) bond length. Both Li(4)-F(3) bond lengths are 2.14 Å. In the fifth Li site, Li(5) is bonded to one O(4), two equivalent O(2), one F(3), and two equivalent F(4) atoms to form LiO3F3 octahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent V(4)O4F2 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one V(4)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Li(5)-O(4) bond length is 2.18 Å. There is one shorter (2.28 Å) and one longer (2.31 Å) Li(5)-O(2) bond length. The Li(5)-F(3) bond length is 1.98 Å. There is one shorter (2.05 Å) and one longer (2.06 Å) Li(5)-F(4) bond length. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(7), one O(8), two equivalent F(1), and two equivalent F(2) atoms. The Li(6)-O(7) bond length is 2.37 Å. The Li(6)-O(8) bond length is 1.89 Å. There is one shorter (2.43 Å) and one longer (2.48 Å) Li(6)-F(1) bond length. There is one shorter (2.03 Å) and one longer (2.04 Å) Li(6)-F(2) bond length. In the seventh Li site, Li(7) is bonded to one O(6), two equivalent O(3), one F(4), and two equivalent F(3) atoms to form LiO3F3 octahedra that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one V(4)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(4)O4F2 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Li(7)-O(6) bond length is 2.17 Å. There is one shorter (2.25 Å) and one longer (2.30 Å) Li(7)-O(3) bond length. The Li(7)-F(4) bond length is 2.10 Å. There is one shorter (2.04 Å) and one longer (2.05 Å) Li(7)-F(3) bond length. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one O(5), two equivalent O(1), two equivalent O(8), and one F(2) atom. The Li(8)-O(5) bond length is 2.32 Å. There is one shorter (2.46 Å) and one longer (2.54 Å) Li(8)-O(1) bond length. Both Li(8)-O(8) bond lengths are 1.94 Å. The Li(8)-F(2) bond length is 2.19 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O3F3 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Li(1)O3F3 octahedra,  an edgeedge with one Li(1)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(7)O3F3 octahedra, edges with two equivalent V(4)O4F2 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. The V(1)-O(2) bond length is 2.08 Å. The V(1)-O(3) bond length is 2.01 Å. There is one shorter (2.04 Å) and one longer (2.10 Å) V(1)-O(4) bond length. There is one shorter (2.03 Å) and one longer (2.09 Å) V(1)-O(6) bond length. In the second V site, V(2) is bonded to one O(1), two equivalent O(5), two equivalent O(7), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(1)O3F3 octahedra, corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(2)O3F3 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent V(4)O4F2 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 3-19°. The V(2)-O(1) bond length is 1.96 Å. There is one shorter (2.01 Å) and one longer (2.07 Å) V(2)-O(5) bond length. There is one shorter (2.04 Å) and one longer (2.12 Å) V(2)-O(7) bond length. The V(2)-F(1) bond length is 2.17 Å. In the third V site, V(3) is bonded to one O(4), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one Li(5)O3F3 octahedra, corners with two equivalent Li(7)O3F3 octahedra,  an edgeedge with one Li(7)O3F3 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. The V(3)-O(4) bond length is 2.03 Å. The V(3)-O(7) bond length is 2.05 Å. There is one shorter (2.03 Å) and one longer (2.09 Å) V(3)-O(1) bond length. There is one shorter (2.04 Å) and one longer (2.10 Å) V(3)-O(3) bond length. In the fourth V site, V(4) is bonded to one O(5), one O(6), two equivalent O(2), and two equivalent F(1) atoms to form VO4F2 octahedra that share  a cornercorner with one Li(7)O3F3 octahedra, corners with two equivalent Li(5)O3F3 octahedra,  an edgeedge with one Li(5)O3F3 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent V(4)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. The V(4)-O(5) bond length is 1.97 Å. The V(4)-O(6) bond length is 1.99 Å. There is one shorter (1.96 Å) and one longer (2.04 Å) V(4)-O(2) bond length. There is one shorter (2.16 Å) and one longer (2.18 Å) V(4)-F(1) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(8), one V(2), and two equivalent V(3) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one F(1)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(8)Li6 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(8)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Li(4), two equivalent Li(5), one V(1), and two equivalent V(4) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(8)Li6 octahedra, corners with two equivalent F(1)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one F(1)Li3V3 octahedra,  an edgeedge with one F(4)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(7), one V(1), and two equivalent V(3) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth O site, O(4) is bonded to one Li(5), two equivalent Li(1), one V(3), and two equivalent V(1) atoms 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(6)Li3V3 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the fifth O site, O(5) is bonded to one Li(8), two equivalent Li(4), one V(4), and two equivalent V(2) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with two equivalent O(7)Li3V3 octahedra, corners with two equivalent F(3)Li6 octahedra,  an edgeedge with one O(7)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, and edges with two equivalent F(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 9-22°. In the sixth O site, O(6) is bonded to one Li(7), two equivalent Li(3), one V(4), and two equivalent V(1) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra,  a cornercorner with one F(4)Li6 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(8)Li6 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(8)Li6 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent F(1)Li3V3 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 2-17°. In the seventh O site, O(7) is bonded to one Li(6), two equivalent Li(2), one V(3), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(8)Li6 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent F(4)Li6 octahedra,  an edgeedge with one O(5)Li3V3 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, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent F(1)Li3V3 octahedra, and edges with two equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 1-16°. In the eighth O site, O(8) is bonded to one Li(4), one Li(6), two equivalent Li(3), and two equivalent Li(8) atoms to form OLi6 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(7)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, edges with two equivalent F(1)Li3V3 octahedra, edges with two equivalent F(2)Li6 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 7-17°. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), two equivalent Li(6), one V(2), and two equivalent V(4) atoms to form FLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with two equivalent O(2)Li3V3 octahedra, corners with two equivalent F(2)Li6 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one F(2)Li6 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, and edges with two equivalent F(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-23°. In the second F site, F(2) is bonded to one Li(2), one Li(8), two equivalent Li(1), and two equivalent Li(6) atoms to form FLi6 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(5)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent F(1)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one F(1)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(7)Li3V3 octahedra, edges with two equivalent O(8)Li6 octahedra, edges with two equivalent F(2)Li6 octahedra, and edges with two equivalent F(4)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-22°. In the third F site, F(3) is bonded to one Li(3), one Li(5), two equivalent Li(4), and two equivalent Li(7) atoms to form FLi6 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one F(1)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(8)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 6-23°. In the fourth F site, F(4) is bonded to one Li(1), one Li(7), two equivalent Li(2), and two equivalent Li(5) atoms to form FLi6 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(6)Li3V3 octahedra, corners with two equivalent O(2)Li3V3 octahedra, corners with two equivalent O(7)Li3V3 octahedra,  an edgeedge with one O(2)Li3V3 octahedra,  an edgeedge with one O(7)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(2)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 4-9°.