Li2V3O6 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with five equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-19°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second V site, V(2) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form VO6 octahedra that share corners with five equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra, corners with four equivalent O(3)Li2V3 square pyramids,  a cornercorner with one O(2)LiV3 trigonal pyramid, edges with four equivalent O(1)Li3V3 octahedra, edges with four equivalent O(3)Li2V3 square pyramids, and edges with four equivalent O(2)LiV3 trigonal pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form OLiV3 trigonal pyramids that share  a cornercorner with one O(1)Li3V3 octahedra, corners with five equivalent O(3)Li2V3 square pyramids, corners with four equivalent O(2)LiV3 trigonal pyramids, edges with four equivalent O(1)Li3V3 octahedra, and  an edgeedge with one O(2)LiV3 trigonal pyramid. The corner-sharing octahedral tilt angles are 8°. In the third O site, O(3) is bonded to two equivalent Li(1) and three equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(1)Li3V3 octahedra, corners with five equivalent O(2)LiV3 trigonal pyramids, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(3)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 6-7°.
Li2V3O6 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with five equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-19°. The Li(1)-O(2) bond length is 2.02 Å. Both Li(1)-O(3) bond lengths are 2.11 Å. There are two shorter (2.31 Å) and one longer (2.32 Å) Li(1)-O(1) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both V(1)-O(1) bond lengths are 1.92 Å. All V(1)-O(2) bond lengths are 1.99 Å. In the second V site, V(2) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form VO6 octahedra that share corners with five equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. The V(2)-O(2) bond length is 2.01 Å. There is one shorter (2.12 Å) and one longer (2.14 Å) V(2)-O(1) bond length. There are a spread of V(2)-O(3) bond distances ranging from 2.02-2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra, corners with four equivalent O(3)Li2V3 square pyramids,  a cornercorner with one O(2)LiV3 trigonal pyramid, edges with four equivalent O(1)Li3V3 octahedra, edges with four equivalent O(3)Li2V3 square pyramids, and edges with four equivalent O(2)LiV3 trigonal pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form OLiV3 trigonal pyramids that share  a cornercorner with one O(1)Li3V3 octahedra, corners with five equivalent O(3)Li2V3 square pyramids, corners with four equivalent O(2)LiV3 trigonal pyramids, edges with four equivalent O(1)Li3V3 octahedra, and  an edgeedge with one O(2)LiV3 trigonal pyramid. The corner-sharing octahedral tilt angles are 8°. In the third O site, O(3) is bonded to two equivalent Li(1) and three equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(1)Li3V3 octahedra, corners with five equivalent O(2)LiV3 trigonal pyramids, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(3)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 6-7°.