Li2V3O6 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 6-8°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 5-11°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 8-11°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 6-10°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 5-7°. There are three 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 corner and edge-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 corner and edge-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 corner and edge-sharing OLi2V3 square pyramids.
Li2V3O6 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 6-8°. Both Li(1)-O(1) bond lengths are 2.19 Å. Both Li(1)-O(2) bond lengths are 2.25 Å. Both Li(1)-O(3) bond lengths are 2.18 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 5-11°. Both Li(2)-O(1) bond lengths are 2.24 Å. Both Li(2)-O(2) bond lengths are 2.19 Å. Both Li(2)-O(3) bond lengths are 2.13 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 8-11°. Both V(1)-O(1) bond lengths are 2.00 Å. Both V(1)-O(2) bond lengths are 2.09 Å. Both V(1)-O(3) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 6-10°. Both V(2)-O(1) bond lengths are 2.04 Å. Both V(2)-O(2) bond lengths are 2.05 Å. Both V(2)-O(3) bond lengths are 2.06 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms 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 5-7°. Both V(3)-O(1) bond lengths are 2.01 Å. Both V(3)-O(2) bond lengths are 1.94 Å. Both V(3)-O(3) bond lengths are 1.99 Å. There are three 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 corner and edge-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 corner and edge-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 corner and edge-sharing OLi2V3 square pyramids.