Na3CoO3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2) and three equivalent O(1) atoms to form a mixture of corner and edge-sharing NaO5 square pyramids. In the second Na site, Na(2) is bonded to one O(1) and four equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing NaO5 trigonal bipyramids. Co(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1) and two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2), three equivalent Na(1), and one Co(1) atom to form a mixture of corner and edge-sharing ONa5Co octahedra. The corner-sharing octahedral tilt angles are 14°. In the second O site, O(2) is bonded to one Na(1), four equivalent Na(2), and one Co(1) atom to form a mixture of distorted corner and edge-sharing ONa5Co octahedra. The corner-sharing octahedral tilt angles range from 8-33°.
Na3CoO3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2) and three equivalent O(1) atoms to form a mixture of corner and edge-sharing NaO5 square pyramids. Both Na(1)-O(2) bond lengths are 2.57 Å. There is one shorter (2.28 Å) and two longer (2.37 Å) Na(1)-O(1) bond lengths. In the second Na site, Na(2) is bonded to one O(1) and four equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing NaO5 trigonal bipyramids. The Na(2)-O(1) bond length is 2.28 Å. There are a spread of Na(2)-O(2) bond distances ranging from 2.37-2.46 Å. Co(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1) and two equivalent O(2) atoms. The Co(1)-O(1) bond length is 1.76 Å. Both Co(1)-O(2) bond lengths are 1.71 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2), three equivalent Na(1), and one Co(1) atom to form a mixture of corner and edge-sharing ONa5Co octahedra. The corner-sharing octahedral tilt angles are 14°. In the second O site, O(2) is bonded to one Na(1), four equivalent Na(2), and one Co(1) atom to form a mixture of distorted corner and edge-sharing ONa5Co octahedra. The corner-sharing octahedral tilt angles range from 8-33°.