Na(CoO2)3 is Ilmenite-like structured and crystallizes in the trigonal R3 space group. Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of edge and corner-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 30-48°. In the second Co site, Co(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of distorted corner and face-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 30-55°. In the third Co site, Co(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of edge, corner, and face-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Co(1), one Co(2), and one Co(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Co(1), one Co(2), and one Co(3) atom.
Na(CoO2)3 is Ilmenite-like structured and crystallizes in the trigonal R3 space group. Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. All Na(1)-O(1) bond lengths are 2.47 Å. All Na(1)-O(2) bond lengths are 2.16 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of edge and corner-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 30-48°. All Co(1)-O(1) bond lengths are 1.97 Å. All Co(1)-O(2) bond lengths are 1.83 Å. In the second Co site, Co(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of distorted corner and face-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 30-55°. All Co(2)-O(1) bond lengths are 1.90 Å. All Co(2)-O(2) bond lengths are 2.18 Å. In the third Co site, Co(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of edge, corner, and face-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles are 55°. All Co(3)-O(1) bond lengths are 1.96 Å. All Co(3)-O(2) bond lengths are 1.88 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Co(1), one Co(2), and one Co(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Co(1), one Co(2), and one Co(3) atom.