LiVO2 is Caswellsilverite-like structured and crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with five equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-49°. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with five equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-49°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-49°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with five equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-49°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Li(2), one V(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one V(2), and two equivalent V(1) atoms to form edge-sharing OLi3V3 octahedra. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form edge-sharing OLi3V3 octahedra.
LiVO2 is Caswellsilverite-like structured and crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with five equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-49°. The Li(1)-O(1) bond length is 2.30 Å. The Li(1)-O(3) bond length is 2.11 Å. There is one shorter (2.25 Å) and one longer (2.26 Å) Li(1)-O(2) bond length. There is one shorter (2.14 Å) and one longer (2.15 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with five equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-49°. The Li(2)-O(2) bond length is 2.31 Å. The Li(2)-O(4) bond length is 2.13 Å. There is one shorter (2.23 Å) and one longer (2.24 Å) Li(2)-O(1) bond length. Both Li(2)-O(3) bond lengths are 2.14 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-49°. The V(1)-O(2) bond length is 2.10 Å. The V(1)-O(4) bond length is 2.10 Å. Both V(1)-O(1) bond lengths are 2.04 Å. Both V(1)-O(3) bond lengths are 2.05 Å. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with five equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-49°. The V(2)-O(1) bond length is 2.12 Å. The V(2)-O(3) bond length is 2.12 Å. Both V(2)-O(2) bond lengths are 2.03 Å. Both V(2)-O(4) bond lengths are 2.04 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Li(2), one V(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one V(2), and two equivalent V(1) atoms to form edge-sharing OLi3V3 octahedra. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form edge-sharing OLi3V3 octahedra.