LiV2O3F crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(6), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share corners with two equivalent V(4)O5F octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(2)O5F octahedra, and  a cornercorner with one Li(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 55-64°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(4)O5F octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(2)O5F octahedra, and  a cornercorner with one Li(1)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 56-62°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one F(2) atom to form VO5F octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent V(1)O4F2 octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(4)O5F octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(2)O3F tetrahedra,  an edgeedge with one V(4)O5F octahedra, edges with two equivalent V(1)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. In the fourth V site, V(4) is bonded to one O(2), two equivalent O(4), two equivalent O(5), and one F(2) atom to form VO5F octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(2)O3F tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 7-11°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(4)V5 square pyramid, corners with two equivalent O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra, corners with two equivalent O(3)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(3)LiV3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), and one V(4) atom to form OLiV3 tetrahedra that share  a cornercorner with one O(4)V5 square pyramid,  a cornercorner with one O(5)LiV3 tetrahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(3)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(5)LiV3 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(4)V5 square pyramid, corners with two equivalent O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra, corners with two equivalent O(1)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(1)LiV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one V(1), two equivalent V(3), and two equivalent V(4) atoms to form OV5 square pyramids that share  a cornercorner with one O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra,  a cornercorner with one O(1)LiV3 trigonal pyramid,  a cornercorner with one O(3)LiV3 trigonal pyramid, edges with two equivalent O(4)V5 square pyramids,  an edgeedge with one O(2)LiV3 tetrahedra,  an edgeedge with one O(5)LiV3 tetrahedra,  an edgeedge with one O(1)LiV3 trigonal pyramid, and  an edgeedge with one O(3)LiV3 trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), one V(2), and two equivalent V(4) atoms to form distorted OLiV3 tetrahedra that share corners with two equivalent O(4)V5 square pyramids,  a cornercorner with one O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(3)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(2)LiV3 tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent V(3) atoms. There are two 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 rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(4) atom.
LiV2O3F crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(6), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share corners with two equivalent V(4)O5F octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(2)O5F octahedra, and  a cornercorner with one Li(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 55-64°. The Li(1)-O(2) bond length is 2.00 Å. The Li(1)-O(6) bond length is 1.99 Å. The Li(1)-F(1) bond length is 1.90 Å. The Li(1)-F(2) bond length is 2.01 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent V(4)O5F octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(2)O5F octahedra, and  a cornercorner with one Li(1)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 56-62°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(5) bond length is 2.06 Å. The Li(2)-F(1) bond length is 1.91 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The V(1)-O(1) bond length is 2.01 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 1.96 Å. The V(1)-O(4) bond length is 2.15 Å. The V(1)-F(1) bond length is 2.00 Å. The V(1)-F(2) bond length is 2.25 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one F(2) atom to form VO5F octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent V(1)O4F2 octahedra, edges with two equivalent V(4)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(2) bond length is 2.01 Å. The V(2)-O(3) bond length is 2.05 Å. The V(2)-O(5) bond length is 2.06 Å. The V(2)-O(6) bond length is 2.02 Å. The V(2)-F(2) bond length is 2.17 Å. In the third V site, V(3) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(4)O5F octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(2)O3F tetrahedra,  an edgeedge with one V(4)O5F octahedra, edges with two equivalent V(1)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. The V(3)-O(1) bond length is 2.03 Å. The V(3)-O(3) bond length is 2.02 Å. There is one shorter (2.18 Å) and one longer (2.23 Å) V(3)-O(4) bond length. There is one shorter (1.96 Å) and one longer (2.04 Å) V(3)-O(6) bond length. In the fourth V site, V(4) is bonded to one O(2), two equivalent O(4), two equivalent O(5), and one F(2) atom to form VO5F octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(2)O3F tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, and edges with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 7-11°. The V(4)-O(2) bond length is 2.04 Å. Both V(4)-O(4) bond lengths are 2.12 Å. Both V(4)-O(5) bond lengths are 1.99 Å. The V(4)-F(2) bond length is 2.18 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(4)V5 square pyramid, corners with two equivalent O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra, corners with two equivalent O(3)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(3)LiV3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), and one V(4) atom to form OLiV3 tetrahedra that share  a cornercorner with one O(4)V5 square pyramid,  a cornercorner with one O(5)LiV3 tetrahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(3)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(5)LiV3 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(4)V5 square pyramid, corners with two equivalent O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra, corners with two equivalent O(1)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(1)LiV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one V(1), two equivalent V(3), and two equivalent V(4) atoms to form OV5 square pyramids that share  a cornercorner with one O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra,  a cornercorner with one O(1)LiV3 trigonal pyramid,  a cornercorner with one O(3)LiV3 trigonal pyramid, edges with two equivalent O(4)V5 square pyramids,  an edgeedge with one O(2)LiV3 tetrahedra,  an edgeedge with one O(5)LiV3 tetrahedra,  an edgeedge with one O(1)LiV3 trigonal pyramid, and  an edgeedge with one O(3)LiV3 trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), one V(2), and two equivalent V(4) atoms to form distorted OLiV3 tetrahedra that share corners with two equivalent O(4)V5 square pyramids,  a cornercorner with one O(2)LiV3 tetrahedra, corners with two equivalent O(5)LiV3 tetrahedra, corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent O(3)LiV3 trigonal pyramids,  an edgeedge with one O(4)V5 square pyramid, and  an edgeedge with one O(2)LiV3 tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent V(3) atoms. There are two 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 rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(4) atom.