LiVOF2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(2), and one F(3) atom to form LiOF3 tetrahedra that share corners with three equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O2F4 octahedra, and corners with two equivalent Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 50-63°. In the second Li site, Li(2) is bonded to one O(2), one F(1), one F(2), and one F(4) atom to form LiOF3 tetrahedra that share corners with three equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O2F4 octahedra, and corners with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 50-62°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form VO2F4 octahedra that share corners with four equivalent Li(1)OF3 tetrahedra, corners with four equivalent Li(2)OF3 tetrahedra, and edges with three equivalent V(2)O4F2 octahedra. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), one F(3), and one F(4) atom to form VO4F2 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent V(2)O4F2 octahedra, and edges with three equivalent V(1)O2F4 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. In the second O site, O(2) is bonded to one Li(2), one V(1), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom.
LiVOF2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(2), and one F(3) atom to form LiOF3 tetrahedra that share corners with three equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O2F4 octahedra, and corners with two equivalent Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 50-63°. The Li(1)-O(1) bond length is 1.97 Å. The Li(1)-F(1) bond length is 1.91 Å. The Li(1)-F(2) bond length is 1.91 Å. The Li(1)-F(3) bond length is 1.93 Å. In the second Li site, Li(2) is bonded to one O(2), one F(1), one F(2), and one F(4) atom to form LiOF3 tetrahedra that share corners with three equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O2F4 octahedra, and corners with two equivalent Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 50-62°. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-F(1) bond length is 1.92 Å. The Li(2)-F(2) bond length is 1.92 Å. The Li(2)-F(4) bond length is 1.92 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form VO2F4 octahedra that share corners with four equivalent Li(1)OF3 tetrahedra, corners with four equivalent Li(2)OF3 tetrahedra, and edges with three equivalent V(2)O4F2 octahedra. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-F(1) bond length is 1.99 Å. The V(1)-F(2) bond length is 1.99 Å. The V(1)-F(3) bond length is 2.08 Å. The V(1)-F(4) bond length is 2.06 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), one F(3), and one F(4) atom to form VO4F2 octahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent V(2)O4F2 octahedra, and edges with three equivalent V(1)O2F4 octahedra. There is one shorter (1.99 Å) and one longer (2.04 Å) V(2)-O(1) bond length. There is one shorter (2.02 Å) and one longer (2.06 Å) V(2)-O(2) bond length. The V(2)-F(3) bond length is 2.08 Å. The V(2)-F(4) bond length is 2.09 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. In the second O site, O(2) is bonded to one Li(2), one V(1), and two equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom.