LiVF5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(2), one F(4), and one F(5) atom. V(1) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 39°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 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 two equivalent V(1) atoms. 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 water-like geometry to one Li(1) and one V(1) atom.
LiVF5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(2), one F(4), and one F(5) atom. The Li(1)-F(1) bond length is 1.84 Å. The Li(1)-F(2) bond length is 2.02 Å. The Li(1)-F(4) bond length is 2.06 Å. The Li(1)-F(5) bond length is 2.00 Å. V(1) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 39°. The V(1)-F(1) bond length is 1.83 Å. The V(1)-F(2) bond length is 1.85 Å. The V(1)-F(4) bond length is 1.85 Å. The V(1)-F(5) bond length is 1.86 Å. There is one shorter (1.98 Å) and one longer (2.00 Å) V(1)-F(3) 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(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 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 two equivalent V(1) atoms. 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 water-like geometry to one Li(1) and one V(1) atom.