Na(CoO2)3 crystallizes in the triclinic P1 space group. Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and two equivalent O(1) atoms. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(2)O4 tetrahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles are 36°. In the second Co site, Co(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted CoO4 tetrahedra that share corners with four equivalent Co(3)O6 octahedra and corners with three equivalent Co(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 33-71°. In the third Co site, Co(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with four equivalent Co(2)O4 tetrahedra,  a cornercorner with one Co(1)O5 trigonal bipyramid, and edges with two equivalent Co(1)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Co(1), one Co(2), and one Co(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Co(1), and one Co(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Co(2), one Co(3), and one O(6) atom. In the fourth O site, O(4) is bonded to one Na(1), one Co(1), one Co(2), and one Co(3) atom to form corner-sharing ONaCo3 tetrahedra. In the fifth O site, O(5) is bonded to one Na(1), one Co(1), one Co(2), and one Co(3) atom to form distorted corner-sharing ONaCo3 tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Co(1), one Co(3), and one O(3) atom.
Na(CoO2)3 crystallizes in the triclinic P1 space group. Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and two equivalent O(1) atoms. The Na(1)-O(2) bond length is 2.28 Å. The Na(1)-O(3) bond length is 2.92 Å. The Na(1)-O(4) bond length is 2.31 Å. The Na(1)-O(5) bond length is 2.41 Å. The Na(1)-O(6) bond length is 2.41 Å. There is one shorter (2.43 Å) and one longer (2.69 Å) Na(1)-O(1) bond length. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(2)O4 tetrahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles are 36°. The Co(1)-O(1) bond length is 2.21 Å. The Co(1)-O(2) bond length is 1.75 Å. The Co(1)-O(4) bond length is 1.93 Å. The Co(1)-O(5) bond length is 1.97 Å. The Co(1)-O(6) bond length is 2.06 Å. In the second Co site, Co(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted CoO4 tetrahedra that share corners with four equivalent Co(3)O6 octahedra and corners with three equivalent Co(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 33-71°. The Co(2)-O(1) bond length is 1.79 Å. The Co(2)-O(3) bond length is 1.95 Å. The Co(2)-O(4) bond length is 1.96 Å. The Co(2)-O(5) bond length is 1.88 Å. In the third Co site, Co(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with four equivalent Co(2)O4 tetrahedra,  a cornercorner with one Co(1)O5 trigonal bipyramid, and edges with two equivalent Co(1)O5 trigonal bipyramids. The Co(3)-O(1) bond length is 1.92 Å. The Co(3)-O(2) bond length is 1.86 Å. The Co(3)-O(3) bond length is 2.02 Å. The Co(3)-O(4) bond length is 1.90 Å. The Co(3)-O(5) bond length is 1.96 Å. The Co(3)-O(6) bond length is 1.94 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Co(1), one Co(2), and one Co(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Co(1), and one Co(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Co(2), one Co(3), and one O(6) atom. The O(3)-O(6) bond length is 1.47 Å. In the fourth O site, O(4) is bonded to one Na(1), one Co(1), one Co(2), and one Co(3) atom to form corner-sharing ONaCo3 tetrahedra. In the fifth O site, O(5) is bonded to one Na(1), one Co(1), one Co(2), and one Co(3) atom to form distorted corner-sharing ONaCo3 tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Co(1), one Co(3), and one O(3) atom.