Li2VF5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 6-coordinate geometry to one F(1), two equivalent F(3), and three equivalent F(2) atoms. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 57°. 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)Li3V trigonal pyramids, and edges with four equivalent F(2)Li3V trigonal pyramids. In the second F site, F(2) is bonded to three equivalent Li(1) and one V(1) atom to form distorted FLi3V trigonal pyramids that share  a cornercorner with one F(1)Li2V2 trigonal pyramid, corners with three equivalent F(2)Li3V trigonal pyramids, edges with two equivalent F(1)Li2V2 trigonal pyramids, and edges with two equivalent F(2)Li3V trigonal pyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.
Li2VF5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 6-coordinate geometry to one F(1), two equivalent F(3), and three equivalent F(2) atoms. The Li(1)-F(1) bond length is 2.11 Å. There is one shorter (1.86 Å) and one longer (1.92 Å) Li(1)-F(3) bond length. There are a spread of Li(1)-F(2) bond distances ranging from 1.98-2.30 Å. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 57°. Both V(1)-F(1) bond lengths are 2.02 Å. Both V(1)-F(2) bond lengths are 1.92 Å. Both V(1)-F(3) bond lengths are 1.91 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)Li3V trigonal pyramids, and edges with four equivalent F(2)Li3V trigonal pyramids. In the second F site, F(2) is bonded to three equivalent Li(1) and one V(1) atom to form distorted FLi3V trigonal pyramids that share  a cornercorner with one F(1)Li2V2 trigonal pyramid, corners with three equivalent F(2)Li3V trigonal pyramids, edges with two equivalent F(1)Li2V2 trigonal pyramids, and edges with two equivalent F(2)Li3V trigonal pyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.