LiVF5 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a rectangular see-saw-like geometry to one F(2), one F(3), one F(4), and one F(5) atom. V(1) is bonded to one F(1), one F(2), one F(3), one F(5), and two equivalent F(4) atoms to form edge-sharing VF6 octahedra. There are five 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 an L-shaped geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a water-like geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a bent 120 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 in a rectangular see-saw-like geometry to one F(2), one F(3), one F(4), and one F(5) atom. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(3) bond length is 2.03 Å. The Li(1)-F(4) bond length is 2.07 Å. The Li(1)-F(5) bond length is 1.91 Å. V(1) is bonded to one F(1), one F(2), one F(3), one F(5), and two equivalent F(4) atoms to form edge-sharing VF6 octahedra. The V(1)-F(1) bond length is 1.76 Å. The V(1)-F(2) bond length is 1.87 Å. The V(1)-F(3) bond length is 1.83 Å. The V(1)-F(5) bond length is 1.87 Å. There is one shorter (2.03 Å) and one longer (2.10 Å) V(1)-F(4) bond length. There are five 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 an L-shaped geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a water-like geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom.