LiV2O2F3 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms. V(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. 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 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms. Both Li(1)-O(1) bond lengths are 2.28 Å. Both Li(1)-F(1) bond lengths are 2.00 Å. Both Li(1)-F(2) bond lengths are 2.08 Å. V(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. There are two shorter (1.97 Å) and one longer (2.04 Å) V(1)-O(1) bond length. The V(1)-F(2) bond length is 2.12 Å. Both V(1)-F(1) bond lengths are 2.05 Å. 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.