LiLa4CoO8 is (La,Ba)CuO4-derived structured and crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to two equivalent O(1), three equivalent O(2), and four equivalent O(3) atoms. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent O(2), three equivalent O(1), and four equivalent O(3) atoms. Co(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra. The corner-sharing octahedra are not tilted. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent La(1), and three equivalent La(2) atoms to form distorted OLiLa5 octahedra that share corners with five equivalent O(1)LiLa5 octahedra, corners with twelve equivalent O(3)LiLa4Co octahedra, edges with two equivalent O(1)LiLa5 octahedra, edges with six equivalent O(2)La5Co octahedra, and faces with four equivalent O(3)LiLa4Co octahedra. The corner-sharing octahedral tilt angles range from 0-51°. In the second O site, O(2) is bonded to two equivalent La(2), three equivalent La(1), and one Co(1) atom to form distorted OLa5Co octahedra that share corners with five equivalent O(2)La5Co octahedra, corners with twelve equivalent O(3)LiLa4Co octahedra, edges with two equivalent O(2)La5Co octahedra, edges with six equivalent O(1)LiLa5 octahedra, and faces with four equivalent O(3)LiLa4Co octahedra. The corner-sharing octahedral tilt angles range from 0-50°. In the third O site, O(3) is bonded to one Li(1), two equivalent La(1), two equivalent La(2), and one Co(1) atom to form distorted OLiLa4Co octahedra that share corners with two equivalent O(3)LiLa4Co octahedra, corners with six equivalent O(2)La5Co octahedra, corners with six equivalent O(1)LiLa5 octahedra, edges with two equivalent O(3)LiLa4Co octahedra, faces with two equivalent O(2)La5Co octahedra, faces with two equivalent O(1)LiLa5 octahedra, and faces with four equivalent O(3)LiLa4Co octahedra. The corner-sharing octahedral tilt angles range from 0-51°.
LiLa4CoO8 is (La,Ba)CuO4-derived structured and crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedra are not tilted. Both Li(1)-O(1) bond lengths are 2.36 Å. All Li(1)-O(3) bond lengths are 1.93 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to two equivalent O(1), three equivalent O(2), and four equivalent O(3) atoms. Both La(1)-O(1) bond lengths are 2.73 Å. There is one shorter (2.38 Å) and two longer (2.72 Å) La(1)-O(2) bond lengths. All La(1)-O(3) bond lengths are 2.59 Å. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent O(2), three equivalent O(1), and four equivalent O(3) atoms. Both La(2)-O(2) bond lengths are 2.73 Å. There is one shorter (2.34 Å) and two longer (2.73 Å) La(2)-O(1) bond lengths. All La(2)-O(3) bond lengths are 2.61 Å. Co(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra. The corner-sharing octahedra are not tilted. Both Co(1)-O(2) bond lengths are 2.33 Å. All Co(1)-O(3) bond lengths are 1.85 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent La(1), and three equivalent La(2) atoms to form distorted OLiLa5 octahedra that share corners with five equivalent O(1)LiLa5 octahedra, corners with twelve equivalent O(3)LiLa4Co octahedra, edges with two equivalent O(1)LiLa5 octahedra, edges with six equivalent O(2)La5Co octahedra, and faces with four equivalent O(3)LiLa4Co octahedra. The corner-sharing octahedral tilt angles range from 0-51°. In the second O site, O(2) is bonded to two equivalent La(2), three equivalent La(1), and one Co(1) atom to form distorted OLa5Co octahedra that share corners with five equivalent O(2)La5Co octahedra, corners with twelve equivalent O(3)LiLa4Co octahedra, edges with two equivalent O(2)La5Co octahedra, edges with six equivalent O(1)LiLa5 octahedra, and faces with four equivalent O(3)LiLa4Co octahedra. The corner-sharing octahedral tilt angles range from 0-50°. In the third O site, O(3) is bonded to one Li(1), two equivalent La(1), two equivalent La(2), and one Co(1) atom to form distorted OLiLa4Co octahedra that share corners with two equivalent O(3)LiLa4Co octahedra, corners with six equivalent O(2)La5Co octahedra, corners with six equivalent O(1)LiLa5 octahedra, edges with two equivalent O(3)LiLa4Co octahedra, faces with two equivalent O(2)La5Co octahedra, faces with two equivalent O(1)LiLa5 octahedra, and faces with four equivalent O(3)LiLa4Co octahedra. The corner-sharing octahedral tilt angles range from 0-51°.