Li2VOF3 crystallizes in the orthorhombic Pnc2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form LiO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra,  an edgeedge with one V(2)O2F4 octahedra, and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 55°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent F(2) atoms. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form VO2F4 octahedra that share edges with two equivalent Li(1)O2F4 octahedra and edges with two 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(3) atoms to form VO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra,  an edgeedge with one Li(1)O2F4 octahedra, and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 55°. O(1) is bonded to one Li(1), one Li(3), one V(1), and one V(2) atom to form a mixture of corner and edge-sharing OLi2V2 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one V(1), and one V(2) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(4), and one V(2) atom.
Li2VOF3 crystallizes in the orthorhombic Pnc2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form LiO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra,  an edgeedge with one V(2)O2F4 octahedra, and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 55°. Both Li(1)-O(1) bond lengths are 2.19 Å. Both Li(1)-F(2) bond lengths are 2.04 Å. Both Li(1)-F(3) bond lengths are 2.09 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Li(2)-F(1) bond lengths are 1.91 Å. Both Li(2)-F(2) bond lengths are 2.29 Å. Both Li(2)-F(3) bond lengths are 2.23 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent F(2) atoms. Both Li(3)-O(1) bond lengths are 1.93 Å. Both Li(3)-F(2) bond lengths are 2.34 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Li(4)-F(1) bond lengths are 2.34 Å. Both Li(4)-F(2) bond lengths are 1.90 Å. Both Li(4)-F(3) bond lengths are 2.02 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form VO2F4 octahedra that share edges with two equivalent Li(1)O2F4 octahedra and edges with two equivalent V(2)O2F4 octahedra. Both V(1)-O(1) bond lengths are 1.95 Å. Both V(1)-F(1) bond lengths are 2.08 Å. Both V(1)-F(2) bond lengths are 2.04 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(1)O2F4 octahedra,  an edgeedge with one Li(1)O2F4 octahedra, and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 55°. Both V(2)-O(1) bond lengths are 1.93 Å. Both V(2)-F(1) bond lengths are 2.08 Å. Both V(2)-F(3) bond lengths are 2.08 Å. O(1) is bonded to one Li(1), one Li(3), one V(1), and one V(2) atom to form a mixture of corner and edge-sharing OLi2V2 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one V(1), and one V(2) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(4), and one V(2) atom.