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 distorted trigonal planar geometry to one F(3) and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(1) atoms. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 25-48°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar 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 two equivalent V(1) atoms.
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 distorted trigonal planar geometry to one F(3) and two equivalent F(2) atoms. The Li(1)-F(3) bond length is 1.91 Å. Both Li(1)-F(2) bond lengths are 1.86 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(1) atoms. The Li(2)-F(4) bond length is 2.18 Å. Both Li(2)-F(1) bond lengths are 1.88 Å. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 25-48°. The V(1)-F(1) bond length is 1.90 Å. The V(1)-F(2) bond length is 1.92 Å. The V(1)-F(3) bond length is 2.07 Å. The V(1)-F(4) bond length is 2.07 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) V(1)-F(5) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar 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 two equivalent V(1) atoms.