LiVF5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiF5 square pyramids that share corners with five equivalent V(1)F5 trigonal bipyramids. V(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted VF5 trigonal bipyramids that share corners with five equivalent Li(1)F5 square pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiVF5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiF5 square pyramids that share corners with five equivalent V(1)F5 trigonal bipyramids. The Li(1)-F(3) bond length is 2.05 Å. Both Li(1)-F(1) bond lengths are 2.05 Å. Both Li(1)-F(2) bond lengths are 2.00 Å. V(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted VF5 trigonal bipyramids that share corners with five equivalent Li(1)F5 square pyramids. The V(1)-F(3) bond length is 1.75 Å. Both V(1)-F(1) bond lengths are 1.84 Å. Both V(1)-F(2) bond lengths are 1.85 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.