LiV2F5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. V(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form a mixture of corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 19-53°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted corner-sharing FLi2V2 trigonal pyramids.
LiV2F5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Li(1)-F(1) bond lengths are 2.44 Å. Both Li(1)-F(2) bond lengths are 1.82 Å. Both Li(1)-F(3) bond lengths are 2.20 Å. V(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form a mixture of corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 19-53°. The V(1)-F(3) bond length is 2.10 Å. Both V(1)-F(2) bond lengths are 2.05 Å. There are two shorter (2.08 Å) and one longer (2.15 Å) V(1)-F(1) bond length. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted corner-sharing FLi2V2 trigonal pyramids.