Li3Co4CuO8 is Caswellsilverite-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(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Co(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. 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 Cu(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Co(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the third Co site, Co(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Cu(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Co(3), and one Cu(1) atom to form OLi3Co2Cu octahedra that share corners with six equivalent O(1)Li3Co2Cu octahedra, edges with four equivalent O(3)Li2Co4 octahedra, and edges with eight equivalent O(2)Li2Co3Cu 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 Co(1), one Co(2), one Co(3), and one Cu(1) atom to form OLi2Co3Cu octahedra that share corners with six equivalent O(2)Li2Co3Cu octahedra, edges with four equivalent O(2)Li2Co3Cu octahedra, edges with four equivalent O(3)Li2Co4 octahedra, and edges with four equivalent O(1)Li3Co2Cu octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Co(1), one Co(2), and two equivalent Co(3) atoms to form OLi2Co4 octahedra that share corners with six equivalent O(3)Li2Co4 octahedra, edges with four equivalent O(1)Li3Co2Cu octahedra, and edges with eight equivalent O(2)Li2Co3Cu octahedra. The corner-sharing octahedra are not tilted.
Li3Co4CuO8 is Caswellsilverite-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(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Co(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Both Li(1)-O(1) bond lengths are 2.09 Å. Both Li(1)-O(2) bond lengths are 2.30 Å. Both Li(1)-O(3) bond lengths are 2.10 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 Cu(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(2)-O(1) bond lengths are 2.05 Å. All Li(2)-O(2) bond lengths are 2.04 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Co(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Co(1)-O(3) bond lengths are 1.97 Å. All Co(1)-O(2) bond lengths are 1.99 Å. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Co(2)-O(3) bond lengths are 2.28 Å. All Co(2)-O(2) bond lengths are 2.06 Å. In the third Co site, Co(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Both Co(3)-O(1) bond lengths are 1.94 Å. Both Co(3)-O(2) bond lengths are 1.94 Å. Both Co(3)-O(3) bond lengths are 1.94 Å. Cu(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Cu(1)-O(1) bond lengths are 2.19 Å. All Cu(1)-O(2) bond lengths are 2.01 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Co(3), and one Cu(1) atom to form OLi3Co2Cu octahedra that share corners with six equivalent O(1)Li3Co2Cu octahedra, edges with four equivalent O(3)Li2Co4 octahedra, and edges with eight equivalent O(2)Li2Co3Cu 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 Co(1), one Co(2), one Co(3), and one Cu(1) atom to form OLi2Co3Cu octahedra that share corners with six equivalent O(2)Li2Co3Cu octahedra, edges with four equivalent O(2)Li2Co3Cu octahedra, edges with four equivalent O(3)Li2Co4 octahedra, and edges with four equivalent O(1)Li3Co2Cu octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Co(1), one Co(2), and two equivalent Co(3) atoms to form OLi2Co4 octahedra that share corners with six equivalent O(3)Li2Co4 octahedra, edges with four equivalent O(1)Li3Co2Cu octahedra, and edges with eight equivalent O(2)Li2Co3Cu octahedra. The corner-sharing octahedra are not tilted.