Li3V2CoO6 is beta Polonium-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with five equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. Co(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent V(1), and one Co(1) atom to form OLi3V2Co octahedra that share  a cornercorner with one O(1)Li3V2Co octahedra,  a cornercorner with one O(3)Li3VCo2 octahedra, corners with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(2)Li3V3 octahedra, and edges with four equivalent O(3)Li3VCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li3VCo2 octahedra, corners with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(2)Li3V3 octahedra, and edges with four equivalent O(3)Li3VCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent Co(1) atoms to form OLi3VCo2 octahedra that share  a cornercorner with one O(1)Li3V2Co octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with four equivalent O(3)Li3VCo2 octahedra, edges with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(2)Li3V3 octahedra, and edges with four equivalent O(3)Li3VCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.
Li3V2CoO6 is beta Polonium-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Both Li(1)-O(2) bond lengths are 2.16 Å. All Li(1)-O(3) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with five equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. The Li(2)-O(3) bond length is 2.15 Å. Both Li(2)-O(2) bond lengths are 2.23 Å. There is one shorter (2.09 Å) and two longer (2.18 Å) Li(2)-O(1) bond lengths. V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. The V(1)-O(3) bond length is 1.91 Å. Both V(1)-O(1) bond lengths are 2.03 Å. There is one shorter (2.04 Å) and two longer (2.06 Å) V(1)-O(2) bond lengths. Co(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both Co(1)-O(1) bond lengths are 2.09 Å. All Co(1)-O(3) bond lengths are 2.12 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent V(1), and one Co(1) atom to form OLi3V2Co octahedra that share  a cornercorner with one O(1)Li3V2Co octahedra,  a cornercorner with one O(3)Li3VCo2 octahedra, corners with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(2)Li3V3 octahedra, and edges with four equivalent O(3)Li3VCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li3VCo2 octahedra, corners with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(2)Li3V3 octahedra, and edges with four equivalent O(3)Li3VCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent Co(1) atoms to form OLi3VCo2 octahedra that share  a cornercorner with one O(1)Li3V2Co octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with four equivalent O(3)Li3VCo2 octahedra, edges with four equivalent O(1)Li3V2Co octahedra, edges with four equivalent O(2)Li3V3 octahedra, and edges with four equivalent O(3)Li3VCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.