Li2V(OF)2 crystallizes in the monoclinic P2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 7°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form distorted LiO2F4 octahedra that share corners with four equivalent V(1)O4F2 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. V(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. O(1) is bonded to one Li(2), two equivalent Li(1), and two equivalent V(1) atoms to form a mixture of edge and corner-sharing OLi3V2 square pyramids. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom.
Li2V(OF)2 crystallizes in the monoclinic P2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 7°. There are two shorter (2.05 Å) and two longer (2.32 Å) Li(1)-O(1) bond lengths. Both Li(1)-F(1) bond lengths are 1.95 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form distorted LiO2F4 octahedra that share corners with four equivalent V(1)O4F2 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. Both Li(2)-O(1) bond lengths are 2.26 Å. There are two shorter (1.93 Å) and two longer (2.10 Å) Li(2)-F(1) bond lengths. V(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. There are two shorter (1.87 Å) and two longer (1.97 Å) V(1)-O(1) bond lengths. Both V(1)-F(1) bond lengths are 2.04 Å. O(1) is bonded to one Li(2), two equivalent Li(1), and two equivalent V(1) atoms to form a mixture of edge and corner-sharing OLi3V2 square pyramids. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom.