LiVO2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. 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 six equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. There are four 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 six equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with five equivalent O(1)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, edges with three equivalent O(2)Li3V3 octahedra, edges with three equivalent O(3)Li2V3 trigonal bipyramids, edges with three equivalent O(4)Li2V3 trigonal bipyramids, and  a faceface with one O(2)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(3), and one V(4) atom to form OLi3V3 octahedra that share corners with five equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(3)Li2V3 trigonal bipyramids, edges with three equivalent O(4)Li2V3 trigonal bipyramids, and  a faceface with one O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted. 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(4) atom to form distorted OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with three equivalent O(4)Li2V3 trigonal bipyramids, corners with four equivalent O(3)Li2V3 trigonal bipyramids, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(2)Li3V3 octahedra, and  an edgeedge with one O(4)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 86-87°. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), one V(3), and one V(4) atom to form distorted OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with three equivalent O(3)Li2V3 trigonal bipyramids, corners with four equivalent O(4)Li2V3 trigonal bipyramids, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(2)Li3V3 octahedra, and  an edgeedge with one O(3)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 86°.
LiVO2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(1)-O(1) bond length is 2.24 Å. The Li(1)-O(2) bond length is 2.23 Å. The Li(1)-O(3) bond length is 1.84 Å. The Li(1)-O(4) bond length is 1.85 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 six equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Both Li(2)-O(1) bond lengths are 2.22 Å. Both Li(2)-O(2) bond lengths are 2.19 Å. Both Li(2)-O(3) bond lengths are 2.15 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. Both Li(3)-O(1) bond lengths are 2.20 Å. Both Li(3)-O(2) bond lengths are 2.20 Å. Both Li(3)-O(4) bond lengths are 2.15 Å. There are four 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 six equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Both V(1)-O(1) bond lengths are 2.07 Å. Both V(1)-O(2) bond lengths are 2.17 Å. Both V(1)-O(3) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. Both V(2)-O(1) bond lengths are 2.11 Å. Both V(2)-O(3) bond lengths are 2.01 Å. Both V(2)-O(4) bond lengths are 2.02 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. Both V(3)-O(1) bond lengths are 2.15 Å. Both V(3)-O(2) bond lengths are 2.09 Å. Both V(3)-O(4) bond lengths are 2.04 Å. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Both V(4)-O(2) bond lengths are 2.09 Å. Both V(4)-O(3) bond lengths are 2.03 Å. Both V(4)-O(4) bond lengths are 2.02 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with five equivalent O(1)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, edges with three equivalent O(2)Li3V3 octahedra, edges with three equivalent O(3)Li2V3 trigonal bipyramids, edges with three equivalent O(4)Li2V3 trigonal bipyramids, and  a faceface with one O(2)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(3), and one V(4) atom to form OLi3V3 octahedra that share corners with five equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(3)Li2V3 trigonal bipyramids, edges with three equivalent O(4)Li2V3 trigonal bipyramids, and  a faceface with one O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted. 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(4) atom to form distorted OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with three equivalent O(4)Li2V3 trigonal bipyramids, corners with four equivalent O(3)Li2V3 trigonal bipyramids, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(2)Li3V3 octahedra, and  an edgeedge with one O(4)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 86-87°. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), one V(3), and one V(4) atom to form distorted OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li3V3 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with three equivalent O(3)Li2V3 trigonal bipyramids, corners with four equivalent O(4)Li2V3 trigonal bipyramids, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(2)Li3V3 octahedra, and  an edgeedge with one O(3)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 86°.