Li2VF4 crystallizes in the orthorhombic Pbam space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(2) and four equivalent F(1) atoms. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form edge-sharing VF6 octahedra. There are two inequivalent F sites. In the first F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLi2V2 trigonal pyramids. In the second F site, F(1) is bonded in a 5-coordinate geometry to four equivalent Li(1) and one V(1) atom.
Li2VF4 crystallizes in the orthorhombic Pbam space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(2) and four equivalent F(1) atoms. There is one shorter (1.94 Å) and one longer (2.13 Å) Li(1)-F(2) bond length. There are two shorter (1.97 Å) and two longer (2.44 Å) Li(1)-F(1) bond lengths. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form edge-sharing VF6 octahedra. Both V(1)-F(1) bond lengths are 2.11 Å. All V(1)-F(2) bond lengths are 2.13 Å. There are two inequivalent F sites. In the first F site, F(2) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLi2V2 trigonal pyramids. In the second F site, F(1) is bonded in a 5-coordinate geometry to four equivalent Li(1) and one V(1) atom.