LiV2F7 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one F(1), one F(4), one F(5), and one F(6) atom to form LiF4 tetrahedra that share corners with two equivalent V(2)F6 octahedra and corners with three equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form distorted VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra, corners with three equivalent Li(1)F4 tetrahedra, and edges with two equivalent V(2)F6 octahedra. The corner-sharing octahedral tilt angles are 24°. In the second V site, V(2) is bonded to one F(2), one F(3), one F(4), one F(5), and two equivalent F(7) atoms to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles are 24°. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) 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. In the seventh F site, F(7) is bonded in a T-shaped geometry to one V(1) and two equivalent V(2) atoms.
LiV2F7 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one F(1), one F(4), one F(5), and one F(6) atom to form LiF4 tetrahedra that share corners with two equivalent V(2)F6 octahedra and corners with three equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. The Li(1)-F(1) bond length is 1.91 Å. The Li(1)-F(4) bond length is 1.91 Å. The Li(1)-F(5) bond length is 2.01 Å. The Li(1)-F(6) bond length is 1.90 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form distorted VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra, corners with three equivalent Li(1)F4 tetrahedra, and edges with two equivalent V(2)F6 octahedra. The corner-sharing octahedral tilt angles are 24°. The V(1)-F(1) bond length is 1.86 Å. The V(1)-F(2) bond length is 2.05 Å. The V(1)-F(3) bond length is 1.99 Å. The V(1)-F(5) bond length is 2.09 Å. The V(1)-F(6) bond length is 1.88 Å. The V(1)-F(7) bond length is 2.20 Å. In the second V site, V(2) is bonded to one F(2), one F(3), one F(4), one F(5), and two equivalent F(7) atoms to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one V(2)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles are 24°. The V(2)-F(2) bond length is 1.93 Å. The V(2)-F(3) bond length is 1.97 Å. The V(2)-F(4) bond length is 1.87 Å. The V(2)-F(5) bond length is 2.04 Å. There is one shorter (2.05 Å) and one longer (2.13 Å) V(2)-F(7) bond length. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) 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. In the seventh F site, F(7) is bonded in a T-shaped geometry to one V(1) and two equivalent V(2) atoms.