Li2V3O6 crystallizes in the monoclinic C2 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  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(6)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. 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  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(6)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 9-10°. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 8-10°. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 6-8°. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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(5)O6 octahedra, and edges with three equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. In the fifth V site, V(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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(4)O6 octahedra, and edges with three equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. In the sixth V site, V(6) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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(4)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 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(4), one V(5), and one V(6) 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(4), one V(5), and one V(6) atom to form a mixture of corner and edge-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 corner and edge-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(4), one V(5), and one V(6) atom to form a mixture of corner and edge-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 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 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  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(6)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. The Li(1)-O(1) bond length is 2.21 Å. The Li(1)-O(2) bond length is 2.19 Å. The Li(1)-O(3) bond length is 2.13 Å. The Li(1)-O(4) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.24 Å. The Li(1)-O(6) bond length is 2.17 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  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(6)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. The Li(2)-O(1) bond length is 2.22 Å. The Li(2)-O(2) bond length is 2.29 Å. The Li(2)-O(3) bond length is 2.23 Å. The Li(2)-O(4) bond length is 2.18 Å. The Li(2)-O(5) bond length is 2.13 Å. The Li(2)-O(6) bond length is 2.15 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 9-10°. Both V(1)-O(2) bond lengths are 2.00 Å. Both V(1)-O(4) bond lengths are 2.06 Å. Both V(1)-O(6) bond lengths are 2.09 Å. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 8-10°. Both V(2)-O(2) bond lengths are 2.06 Å. Both V(2)-O(4) bond lengths are 2.03 Å. Both V(2)-O(6) bond lengths are 2.06 Å. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 6-8°. Both V(3)-O(2) bond lengths are 1.99 Å. Both V(3)-O(4) bond lengths are 2.01 Å. Both V(3)-O(6) bond lengths are 1.96 Å. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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(5)O6 octahedra, and edges with three equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. Both V(4)-O(1) bond lengths are 1.91 Å. Both V(4)-O(3) bond lengths are 2.03 Å. Both V(4)-O(5) bond lengths are 2.03 Å. In the fifth V site, V(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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(4)O6 octahedra, and edges with three equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both V(5)-O(1) bond lengths are 2.08 Å. Both V(5)-O(3) bond lengths are 2.01 Å. Both V(5)-O(5) bond lengths are 2.06 Å. In the sixth V site, V(6) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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(4)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both V(6)-O(1) bond lengths are 2.08 Å. Both V(6)-O(3) bond lengths are 2.05 Å. Both V(6)-O(5) bond lengths are 2.01 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(4), one V(5), and one V(6) 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(4), one V(5), and one V(6) atom to form a mixture of corner and edge-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 corner and edge-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(4), one V(5), and one V(6) atom to form a mixture of corner and edge-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 corner and edge-sharing OLi2V3 square pyramids.