LiVOF2 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share corners with three equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O2F4 octahedra, and corners with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 51-62°. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent O(1) and two equivalent F(2) atoms to form VO4F2 octahedra that share corners with six equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with three equivalent V(2)O2F4 octahedra. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form VO2F4 octahedra that share corners with eight equivalent Li(1)OF3 tetrahedra and edges with three equivalent V(1)O4F2 octahedra. O(1) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom.
LiVOF2 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share corners with three equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O2F4 octahedra, and corners with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 51-62°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-F(2) bond length is 1.92 Å. Both Li(1)-F(1) bond lengths are 1.92 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to four equivalent O(1) and two equivalent F(2) atoms to form VO4F2 octahedra that share corners with six equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with three equivalent V(2)O2F4 octahedra. There are two shorter (2.03 Å) and two longer (2.04 Å) V(1)-O(1) bond lengths. Both V(1)-F(2) bond lengths are 2.08 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form VO2F4 octahedra that share corners with eight equivalent Li(1)OF3 tetrahedra and edges with three equivalent V(1)O4F2 octahedra. Both V(2)-O(1) bond lengths are 2.00 Å. Both V(2)-F(1) bond lengths are 1.99 Å. Both V(2)-F(2) bond lengths are 2.07 Å. O(1) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom.