Li2V2F7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted body-centered cubic geometry to four equivalent F(2) and four equivalent F(3) atoms. In the second Li site, Li(2) is bonded in a linear geometry to two equivalent F(2) and four equivalent F(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-50°. In the second V site, V(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Li(2), two equivalent Li(1), and one V(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(2) atom.
Li2V2F7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted body-centered cubic geometry to four equivalent F(2) and four equivalent F(3) atoms. All Li(1)-F(2) bond lengths are 2.59 Å. All Li(1)-F(3) bond lengths are 2.49 Å. In the second Li site, Li(2) is bonded in a linear geometry to two equivalent F(2) and four equivalent F(3) atoms. Both Li(2)-F(2) bond lengths are 1.90 Å. All Li(2)-F(3) bond lengths are 2.58 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 38-50°. Both V(1)-F(1) bond lengths are 2.00 Å. All V(1)-F(3) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 50°. Both V(2)-F(2) bond lengths are 2.05 Å. All V(2)-F(3) bond lengths are 2.04 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Li(2), two equivalent Li(1), and one V(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(2) atom.