Li2VO2F crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(4)O2F4 octahedra, corners with three equivalent Li(3)O2F4 octahedra, corners with four equivalent Li(2)O5 square pyramids, edges with three equivalent V(1)O5F octahedra, edges with three equivalent V(2)O5F octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 1-89°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(3)O2F4 octahedra, corners with three equivalent Li(4)O2F4 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with three equivalent V(1)O5F octahedra, edges with three equivalent V(2)O5F octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 1-89°. In the third Li site, Li(3) is bonded to one O(1), one O(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiO2F4 octahedra that share  a cornercorner with one V(1)O5F octahedra, corners with four equivalent Li(4)O2F4 octahedra, corners with two equivalent Li(2)O5 square pyramids, corners with three equivalent Li(1)O5 square pyramids, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiO2F4 octahedra that share  a cornercorner with one V(2)O5F octahedra, corners with four equivalent Li(3)O2F4 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with three equivalent Li(2)O5 square pyramids, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-18°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(3)O2F4 octahedra, corners with four equivalent V(2)O5F octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with three equivalent Li(1)O5 square pyramids, and edges with three equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), two equivalent O(4), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(4)O2F4 octahedra, corners with four equivalent V(1)O5F octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with three equivalent Li(1)O5 square pyramids, and edges with three equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), two equivalent Li(1), one V(1), and one V(2) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra, corners with four equivalent O(2)Li4V2 octahedra,  a cornercorner with one F(1)Li4V square pyramid,  a cornercorner with one F(2)Li4V square pyramid,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with three equivalent O(3)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-13°. In the second O site, O(2) is bonded to one Li(1), one Li(4), two equivalent Li(2), one V(1), and one V(2) atom to form OLi4V2 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra, corners with four equivalent O(1)Li4V2 octahedra,  a cornercorner with one F(1)Li4V square pyramid,  a cornercorner with one F(2)Li4V square pyramid,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with three equivalent O(3)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and two equivalent V(1) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(1)Li4V2 octahedra, corners with four equivalent O(4)Li3V3 octahedra,  a cornercorner with one F(2)Li4V square pyramid, corners with two equivalent F(1)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with three equivalent O(1)Li4V2 octahedra, edges with three equivalent O(2)Li4V2 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one V(1), and two equivalent V(2) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(2)Li4V2 octahedra, corners with four equivalent O(3)Li3V3 octahedra,  a cornercorner with one F(1)Li4V square pyramid, corners with two equivalent F(2)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with three equivalent O(1)Li4V2 octahedra, edges with three equivalent O(2)Li4V2 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-6°. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(3), two equivalent Li(4), and one V(1) atom to form distorted FLi4V square pyramids that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(1)Li4V2 octahedra,  a cornercorner with one O(2)Li4V2 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with four equivalent F(2)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent F(1)Li4V square pyramids, and edges with two equivalent F(2)Li4V square pyramids. The corner-sharing octahedral tilt angles range from 1-90°. In the second F site, F(2) is bonded to two equivalent Li(3), two equivalent Li(4), and one V(2) atom to form distorted FLi4V square pyramids that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(1)Li4V2 octahedra,  a cornercorner with one O(2)Li4V2 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with four equivalent F(1)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent F(1)Li4V square pyramids, and edges with two equivalent F(2)Li4V square pyramids. The corner-sharing octahedral tilt angles range from 1-90°.
Li2VO2F crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(4)O2F4 octahedra, corners with three equivalent Li(3)O2F4 octahedra, corners with four equivalent Li(2)O5 square pyramids, edges with three equivalent V(1)O5F octahedra, edges with three equivalent V(2)O5F octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 1-89°. The Li(1)-O(2) bond length is 2.05 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.02 Å. There is one shorter (2.04 Å) and one longer (2.18 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(3)O2F4 octahedra, corners with three equivalent Li(4)O2F4 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with three equivalent V(1)O5F octahedra, edges with three equivalent V(2)O5F octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 1-89°. The Li(2)-O(1) bond length is 2.05 Å. The Li(2)-O(3) bond length is 2.01 Å. The Li(2)-O(4) bond length is 2.02 Å. There is one shorter (2.04 Å) and one longer (2.18 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiO2F4 octahedra that share  a cornercorner with one V(1)O5F octahedra, corners with four equivalent Li(4)O2F4 octahedra, corners with two equivalent Li(2)O5 square pyramids, corners with three equivalent Li(1)O5 square pyramids, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-18°. The Li(3)-O(1) bond length is 2.04 Å. The Li(3)-O(3) bond length is 2.55 Å. There is one shorter (2.01 Å) and one longer (2.05 Å) Li(3)-F(1) bond length. There is one shorter (2.02 Å) and one longer (2.06 Å) Li(3)-F(2) bond length. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiO2F4 octahedra that share  a cornercorner with one V(2)O5F octahedra, corners with four equivalent Li(3)O2F4 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with three equivalent Li(2)O5 square pyramids, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-18°. The Li(4)-O(2) bond length is 2.04 Å. The Li(4)-O(4) bond length is 2.56 Å. There is one shorter (2.01 Å) and one longer (2.05 Å) Li(4)-F(1) bond length. There is one shorter (2.02 Å) and one longer (2.05 Å) Li(4)-F(2) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(3)O2F4 octahedra, corners with four equivalent V(2)O5F octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with three equivalent Li(1)O5 square pyramids, and edges with three equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. 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(4) bond length is 2.03 Å. There is one shorter (2.04 Å) and one longer (2.12 Å) V(1)-O(3) bond length. The V(1)-F(1) bond length is 2.14 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), two equivalent O(4), and one F(2) atom to form VO5F octahedra that share  a cornercorner with one Li(4)O2F4 octahedra, corners with four equivalent V(1)O5F octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(2)O5F octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with three equivalent Li(1)O5 square pyramids, and edges with three equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. 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 2.03 Å. There is one shorter (2.03 Å) and one longer (2.12 Å) V(2)-O(4) bond length. The V(2)-F(2) bond length is 2.13 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), two equivalent Li(1), one V(1), and one V(2) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra, corners with four equivalent O(2)Li4V2 octahedra,  a cornercorner with one F(1)Li4V square pyramid,  a cornercorner with one F(2)Li4V square pyramid,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with three equivalent O(3)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-13°. In the second O site, O(2) is bonded to one Li(1), one Li(4), two equivalent Li(2), one V(1), and one V(2) atom to form OLi4V2 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra, corners with four equivalent O(1)Li4V2 octahedra,  a cornercorner with one F(1)Li4V square pyramid,  a cornercorner with one F(2)Li4V square pyramid,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with three equivalent O(3)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and two equivalent V(1) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(1)Li4V2 octahedra, corners with four equivalent O(4)Li3V3 octahedra,  a cornercorner with one F(2)Li4V square pyramid, corners with two equivalent F(1)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with three equivalent O(1)Li4V2 octahedra, edges with three equivalent O(2)Li4V2 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one V(1), and two equivalent V(2) atoms to form distorted OLi3V3 octahedra that share  a cornercorner with one O(2)Li4V2 octahedra, corners with four equivalent O(3)Li3V3 octahedra,  a cornercorner with one F(1)Li4V square pyramid, corners with two equivalent F(2)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with three equivalent O(1)Li4V2 octahedra, edges with three equivalent O(2)Li4V2 octahedra,  an edgeedge with one F(1)Li4V square pyramid, and  an edgeedge with one F(2)Li4V square pyramid. The corner-sharing octahedral tilt angles range from 0-6°. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(3), two equivalent Li(4), and one V(1) atom to form distorted FLi4V square pyramids that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(1)Li4V2 octahedra,  a cornercorner with one O(2)Li4V2 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with four equivalent F(2)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent F(1)Li4V square pyramids, and edges with two equivalent F(2)Li4V square pyramids. The corner-sharing octahedral tilt angles range from 1-90°. In the second F site, F(2) is bonded to two equivalent Li(3), two equivalent Li(4), and one V(2) atom to form distorted FLi4V square pyramids that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(1)Li4V2 octahedra,  a cornercorner with one O(2)Li4V2 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with four equivalent F(1)Li4V square pyramids,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(1)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent F(1)Li4V square pyramids, and edges with two equivalent F(2)Li4V square pyramids. The corner-sharing octahedral tilt angles range from 1-90°.