Li2V3O3F5 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(1), one F(2), and one F(3) atom to form LiOF3 tetrahedra that share corners with three equivalent V(1)O2F4 octahedra, corners with three equivalent V(2)O3F3 octahedra, and corners with three equivalent V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 54-65°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one F(4), and one F(5) atom to form LiO2F2 tetrahedra that share corners with three equivalent V(1)O2F4 octahedra, corners with three equivalent V(2)O3F3 octahedra, and corners with three equivalent V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-60°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(2)O3F3 octahedra, and edges with two equivalent V(3)O3F3 octahedra. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(5) atom to form VO3F3 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(1)O2F4 octahedra, and edges with two equivalent V(3)O3F3 octahedra. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(4) atom to form VO3F3 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(1)O2F4 octahedra, and edges with two equivalent V(2)O3F3 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form corner-sharing OLiV3 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted corner-sharing OLiV3 trigonal pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom.
Li2V3O3F5 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(1), one F(2), and one F(3) atom to form LiOF3 tetrahedra that share corners with three equivalent V(1)O2F4 octahedra, corners with three equivalent V(2)O3F3 octahedra, and corners with three equivalent V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 54-65°. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(2) bond length is 1.96 Å. The Li(1)-F(3) bond length is 1.96 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one F(4), and one F(5) atom to form LiO2F2 tetrahedra that share corners with three equivalent V(1)O2F4 octahedra, corners with three equivalent V(2)O3F3 octahedra, and corners with three equivalent V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-60°. The Li(2)-O(1) bond length is 1.92 Å. The Li(2)-O(3) bond length is 1.98 Å. The Li(2)-F(4) bond length is 1.97 Å. The Li(2)-F(5) bond length is 1.98 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(2)O3F3 octahedra, and edges with two equivalent V(3)O3F3 octahedra. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(3) bond length is 2.04 Å. The V(1)-F(4) bond length is 2.05 Å. The V(1)-F(5) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(5) atom to form VO3F3 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(1)O2F4 octahedra, and edges with two equivalent V(3)O3F3 octahedra. The V(2)-O(1) bond length is 1.89 Å. The V(2)-O(2) bond length is 2.04 Å. The V(2)-O(3) bond length is 2.03 Å. The V(2)-F(1) bond length is 2.12 Å. The V(2)-F(2) bond length is 2.11 Å. The V(2)-F(5) bond length is 2.08 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(4) atom to form VO3F3 octahedra that share corners with three equivalent Li(2)O2F2 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent V(1)O2F4 octahedra, and edges with two equivalent V(2)O3F3 octahedra. The V(3)-O(1) bond length is 1.89 Å. The V(3)-O(2) bond length is 2.04 Å. The V(3)-O(3) bond length is 2.05 Å. The V(3)-F(1) bond length is 2.11 Å. The V(3)-F(3) bond length is 2.10 Å. The V(3)-F(4) bond length is 2.08 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form corner-sharing OLiV3 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted corner-sharing OLiV3 trigonal pyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom.