Li4NbCo3O8 is Caswellsilverite-derived structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, edges with six equivalent Li(2)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. Nb(1) is bonded to six equivalent O(2) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with six equivalent Li(2)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. Co(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2) and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with six equivalent O(1)Li3Co3 octahedra and edges with twelve equivalent O(2)Li3NbCo2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Nb(1), and two equivalent Co(1) atoms to form OLi3NbCo2 octahedra that share corners with six equivalent O(2)Li3NbCo2 octahedra, edges with four equivalent O(1)Li3Co3 octahedra, and edges with eight equivalent O(2)Li3NbCo2 octahedra. The corner-sharing octahedra are not tilted.
Li4NbCo3O8 is Caswellsilverite-derived structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, edges with six equivalent Li(2)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Li(1)-O(2) bond lengths are 2.20 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. Both Li(2)-O(1) bond lengths are 2.26 Å. All Li(2)-O(2) bond lengths are 2.10 Å. Nb(1) is bonded to six equivalent O(2) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with six equivalent Li(2)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Nb(1)-O(2) bond lengths are 2.04 Å. Co(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. Both Co(1)-O(1) bond lengths are 1.99 Å. All Co(1)-O(2) bond lengths are 2.14 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2) and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with six equivalent O(1)Li3Co3 octahedra and edges with twelve equivalent O(2)Li3NbCo2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Nb(1), and two equivalent Co(1) atoms to form OLi3NbCo2 octahedra that share corners with six equivalent O(2)Li3NbCo2 octahedra, edges with four equivalent O(1)Li3Co3 octahedra, and edges with eight equivalent O(2)Li3NbCo2 octahedra. The corner-sharing octahedra are not tilted.