LiV2F9 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent F(4) and two equivalent F(5) atoms. 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 corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. 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 a linear geometry to two equivalent V(1) atoms. In the third F site, F(3) is bonded in a linear geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees 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.
LiV2F9 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent F(4) and two equivalent F(5) atoms. Both Li(1)-F(4) bond lengths are 2.12 Å. Both Li(1)-F(5) bond lengths are 2.06 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 corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The V(1)-F(1) bond length is 1.77 Å. The V(1)-F(3) bond length is 1.96 Å. The V(1)-F(4) bond length is 1.83 Å. The V(1)-F(5) bond length is 1.86 Å. There is one shorter (1.95 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 single-bond geometry to one V(1) atom. In the second F site, F(2) is bonded in a linear geometry to two equivalent V(1) atoms. In the third F site, F(3) is bonded in a linear geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees 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.