LiVF6 crystallizes in the monoclinic Cc space group. Li(1) is bonded to one F(2), one F(3), one F(4), and one F(6) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra. There are six inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to 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. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(1) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiVF6 crystallizes in the monoclinic Cc space group. Li(1) is bonded to one F(2), one F(3), one F(4), and one F(6) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. The Li(1)-F(2) bond length is 1.95 Å. The Li(1)-F(3) bond length is 1.93 Å. The Li(1)-F(4) bond length is 1.93 Å. The Li(1)-F(6) bond length is 1.95 Å. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra. The V(1)-F(1) bond length is 1.77 Å. The V(1)-F(2) bond length is 1.83 Å. The V(1)-F(3) bond length is 1.85 Å. The V(1)-F(4) bond length is 1.83 Å. The V(1)-F(5) bond length is 1.77 Å. The V(1)-F(6) bond length is 1.84 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to 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. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(1) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.