LiV2F5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with six equivalent V(1)F6 octahedra, and edges with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-58°. V(1) is bonded to one F(1), two equivalent F(3), and three equivalent F(2) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and  a faceface with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. There are three inequivalent F sites. In the first F site, F(1) 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 F(1)Li2V2 trigonal pyramids, corners with two equivalent F(2)LiV3 trigonal pyramids, and edges with four equivalent F(2)LiV3 trigonal pyramids. In the second F site, F(2) is bonded to one Li(1) and three equivalent V(1) atoms to form FLiV3 trigonal pyramids that share  a cornercorner with one F(1)Li2V2 trigonal pyramid, corners with three equivalent F(2)LiV3 trigonal pyramids, edges with two equivalent F(1)Li2V2 trigonal pyramids, and edges with two equivalent F(2)LiV3 trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms.
LiV2F5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with six equivalent V(1)F6 octahedra, and edges with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-58°. Both Li(1)-F(1) bond lengths are 2.22 Å. Both Li(1)-F(2) bond lengths are 2.13 Å. Both Li(1)-F(3) bond lengths are 2.03 Å. V(1) is bonded to one F(1), two equivalent F(3), and three equivalent F(2) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and  a faceface with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The V(1)-F(1) bond length is 2.15 Å. There is one shorter (2.07 Å) and one longer (2.08 Å) V(1)-F(3) bond length. There are a spread of V(1)-F(2) bond distances ranging from 2.14-2.23 Å. There are three inequivalent F sites. In the first F site, F(1) 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 F(1)Li2V2 trigonal pyramids, corners with two equivalent F(2)LiV3 trigonal pyramids, and edges with four equivalent F(2)LiV3 trigonal pyramids. In the second F site, F(2) is bonded to one Li(1) and three equivalent V(1) atoms to form FLiV3 trigonal pyramids that share  a cornercorner with one F(1)Li2V2 trigonal pyramid, corners with three equivalent F(2)LiV3 trigonal pyramids, edges with two equivalent F(1)Li2V2 trigonal pyramids, and edges with two equivalent F(2)LiV3 trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms.