LiVOF3 crystallizes in the orthorhombic Pnc2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent F(1) and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra, corners with four equivalent V(1)O2F4 octahedra, and  an edgeedge with one V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form VO2F4 octahedra that share corners with four equivalent Li(2)O2F4 octahedra and edges with two equivalent V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form VO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra,  an edgeedge with one Li(2)O2F4 octahedra, and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 58°. O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded in an L-shaped geometry to one V(1) and one V(2) atom.
LiVOF3 crystallizes in the orthorhombic Pnc2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent F(1) and two equivalent F(2) atoms. Both Li(1)-F(1) bond lengths are 1.85 Å. Both Li(1)-F(2) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra, corners with four equivalent V(1)O2F4 octahedra, and  an edgeedge with one V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. Both Li(2)-O(1) bond lengths are 2.20 Å. Both Li(2)-F(1) bond lengths are 2.26 Å. Both Li(2)-F(2) bond lengths are 2.19 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form VO2F4 octahedra that share corners with four equivalent Li(2)O2F4 octahedra and edges with two equivalent V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both V(1)-O(1) bond lengths are 1.86 Å. Both V(1)-F(2) bond lengths are 1.89 Å. Both V(1)-F(3) bond lengths are 2.05 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form VO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra,  an edgeedge with one Li(2)O2F4 octahedra, and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 58°. Both V(2)-O(1) bond lengths are 1.88 Å. Both V(2)-F(1) bond lengths are 1.92 Å. Both V(2)-F(3) bond lengths are 1.94 Å. O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded in an L-shaped geometry to one V(1) and one V(2) atom.