LiV2O2F3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with six equivalent V(1)O3F3 octahedra, and edges with four equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-61°. V(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(1) atoms to form VO3F3 octahedra that share corners with three equivalent Li(1)O2F4 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and  a faceface with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form OLiV3 trigonal pyramids that share  a cornercorner with one F(2)Li2V2 trigonal pyramid, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with two equivalent O(1)LiV3 trigonal pyramids, and edges with two equivalent F(2)Li2V2 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent F(2)Li2V2 trigonal pyramids, and edges with four equivalent O(1)LiV3 trigonal pyramids.
LiV2O2F3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with six equivalent V(1)O3F3 octahedra, and edges with four equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-61°. Both Li(1)-O(1) bond lengths are 2.18 Å. Both Li(1)-F(1) bond lengths are 2.09 Å. Both Li(1)-F(2) bond lengths are 2.09 Å. V(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(1) atoms to form VO3F3 octahedra that share corners with three equivalent Li(1)O2F4 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and  a faceface with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. There are a spread of V(1)-O(1) bond distances ranging from 1.98-2.04 Å. The V(1)-F(2) bond length is 2.13 Å. There is one shorter (2.01 Å) and one longer (2.07 Å) V(1)-F(1) bond length. O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form OLiV3 trigonal pyramids that share  a cornercorner with one F(2)Li2V2 trigonal pyramid, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with two equivalent O(1)LiV3 trigonal pyramids, and edges with two equivalent F(2)Li2V2 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent O(1)LiV3 trigonal pyramids, corners with two equivalent F(2)Li2V2 trigonal pyramids, and edges with four equivalent O(1)LiV3 trigonal pyramids.