Li2V3O6 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(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids.
Li2V3O6 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(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(1)-O(1) bond length is 2.28 Å. The Li(1)-O(2) bond length is 2.31 Å. The Li(1)-O(3) bond length is 2.19 Å. The Li(1)-O(4) bond length is 2.09 Å. The Li(1)-O(5) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.15 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. The Li(2)-O(1) bond length is 2.13 Å. The Li(2)-O(2) bond length is 2.20 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(4) bond length is 2.25 Å. The Li(2)-O(5) bond length is 2.14 Å. The Li(2)-O(6) bond length is 2.25 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. The V(1)-O(1) bond length is 2.01 Å. The V(1)-O(2) bond length is 2.05 Å. The V(1)-O(3) bond length is 2.10 Å. The V(1)-O(4) bond length is 2.04 Å. The V(1)-O(5) bond length is 2.04 Å. The V(1)-O(6) bond length is 2.07 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. The V(2)-O(1) bond length is 2.03 Å. The V(2)-O(2) bond length is 1.92 Å. The V(2)-O(3) bond length is 1.90 Å. The V(2)-O(4) bond length is 2.05 Å. The V(2)-O(5) bond length is 1.98 Å. The V(2)-O(6) bond length is 2.02 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. The V(3)-O(1) bond length is 2.02 Å. The V(3)-O(2) bond length is 2.07 Å. The V(3)-O(3) bond length is 2.12 Å. The V(3)-O(4) bond length is 2.01 Å. The V(3)-O(5) bond length is 2.09 Å. The V(3)-O(6) bond length is 2.00 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids.