LiVF4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 6-coordinate geometry to one F(2), one F(3), and four equivalent F(1) atoms. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing VF6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms.
LiVF4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 6-coordinate geometry to one F(2), one F(3), and four equivalent F(1) atoms. The Li(1)-F(2) bond length is 2.07 Å. The Li(1)-F(3) bond length is 2.01 Å. There are two shorter (1.95 Å) and two longer (2.49 Å) Li(1)-F(1) bond lengths. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing VF6 octahedra. Both V(1)-F(1) bond lengths are 1.90 Å. Both V(1)-F(2) bond lengths are 2.02 Å. Both V(1)-F(3) bond lengths are 2.04 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms.