Li2VO2F is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), three equivalent O(2), and one F(2) atom to form LiO5F octahedra that share  a cornercorner with one Li(2)O2F4 octahedra,  a cornercorner with one Li(1)O5F octahedra, corners with four equivalent V(1)O5F octahedra, edges with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share  a cornercorner with one Li(1)O5F octahedra,  a cornercorner with one V(1)O5F octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-11°. V(1) is bonded to two equivalent O(2), three equivalent O(1), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(2)O2F4 octahedra,  a cornercorner with one V(1)O5F octahedra, corners with four equivalent Li(1)O5F octahedra, edges with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one F(1)Li4V2 octahedra, corners with five equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. In the second O site, O(2) is bonded to one Li(2), three equivalent Li(1), and two equivalent V(1) atoms to form OLi4V2 octahedra that share  a cornercorner with one F(2)Li6 octahedra, corners with five equivalent O(1)Li3V3 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Li(2) and two equivalent V(1) atoms to form FLi4V2 octahedra that share corners with two equivalent O(1)Li3V3 octahedra, corners with four equivalent F(2)Li6 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles are 6°. In the second F site, F(2) is bonded to two equivalent Li(1) and four equivalent Li(2) atoms to form FLi6 octahedra that share corners with two equivalent O(2)Li4V2 octahedra, corners with four equivalent F(1)Li4V2 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles are 6°.
Li2VO2F is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), three equivalent O(2), and one F(2) atom to form LiO5F octahedra that share  a cornercorner with one Li(2)O2F4 octahedra,  a cornercorner with one Li(1)O5F octahedra, corners with four equivalent V(1)O5F octahedra, edges with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There is one shorter (2.21 Å) and one longer (2.24 Å) Li(1)-O(1) bond length. There are a spread of Li(1)-O(2) bond distances ranging from 2.12-2.16 Å. The Li(1)-F(2) bond length is 2.12 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share  a cornercorner with one Li(1)O5F octahedra,  a cornercorner with one V(1)O5F octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-11°. The Li(2)-O(1) bond length is 2.13 Å. The Li(2)-O(2) bond length is 2.08 Å. There is one shorter (2.20 Å) and one longer (2.21 Å) Li(2)-F(1) bond length. There is one shorter (1.99 Å) and one longer (2.00 Å) Li(2)-F(2) bond length. V(1) is bonded to two equivalent O(2), three equivalent O(1), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(2)O2F4 octahedra,  a cornercorner with one V(1)O5F octahedra, corners with four equivalent Li(1)O5F octahedra, edges with four equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There is one shorter (1.99 Å) and one longer (2.00 Å) V(1)-O(2) bond length. There are a spread of V(1)-O(1) bond distances ranging from 2.05-2.08 Å. The V(1)-F(1) bond length is 2.14 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one F(1)Li4V2 octahedra, corners with five equivalent O(2)Li4V2 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. In the second O site, O(2) is bonded to one Li(2), three equivalent Li(1), and two equivalent V(1) atoms to form OLi4V2 octahedra that share  a cornercorner with one F(2)Li6 octahedra, corners with five equivalent O(1)Li3V3 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Li(2) and two equivalent V(1) atoms to form FLi4V2 octahedra that share corners with two equivalent O(1)Li3V3 octahedra, corners with four equivalent F(2)Li6 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles are 6°. In the second F site, F(2) is bonded to two equivalent Li(1) and four equivalent Li(2) atoms to form FLi6 octahedra that share corners with two equivalent O(2)Li4V2 octahedra, corners with four equivalent F(1)Li4V2 octahedra, edges with two equivalent F(1)Li4V2 octahedra, edges with two equivalent F(2)Li6 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles are 6°.