LiVF5 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(3), one F(4), and one F(5) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 13-55°. V(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. There are five 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 two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiVF5 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(3), one F(4), and one F(5) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 13-55°. The Li(1)-F(1) bond length is 1.94 Å. The Li(1)-F(3) bond length is 1.98 Å. The Li(1)-F(4) bond length is 1.88 Å. The Li(1)-F(5) bond length is 1.94 Å. V(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. The V(1)-F(1) bond length is 1.83 Å. The V(1)-F(3) bond length is 1.87 Å. The V(1)-F(4) bond length is 1.86 Å. The V(1)-F(5) bond length is 1.83 Å. There is one shorter (1.96 Å) and one longer (1.97 Å) V(1)-F(2) bond length. There are five 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 two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.