LiVF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one F(2) and two equivalent F(5) atoms. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one F(4) and two equivalent F(3) atoms. V(1) is bonded to one F(2), one F(3), one F(4), one F(5), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiVF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one F(2) and two equivalent F(5) atoms. The Li(1)-F(2) bond length is 1.92 Å. Both Li(1)-F(5) bond lengths are 1.86 Å. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one F(4) and two equivalent F(3) atoms. The Li(2)-F(4) bond length is 1.90 Å. Both Li(2)-F(3) bond lengths are 1.85 Å. V(1) is bonded to one F(2), one F(3), one F(4), one F(5), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 9°. The V(1)-F(2) bond length is 2.07 Å. The V(1)-F(3) bond length is 1.91 Å. The V(1)-F(4) bond length is 2.08 Å. The V(1)-F(5) bond length is 1.89 Å. There is one shorter (1.96 Å) and one longer (1.98 Å) V(1)-F(1) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.