NaCoO2 is Caswellsilverite-like structured and crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, edges with six equivalent Na(1)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°. Co(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with six equivalent Na(1)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and four equivalent Co(1) atoms to form ONa2Co4 octahedra that share corners with two equivalent O(1)Na2Co4 octahedra, corners with four equivalent O(2)Na4Co2 octahedra, edges with six equivalent O(1)Na2Co4 octahedra, and edges with six equivalent O(2)Na4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second O site, O(2) is bonded to four equivalent Na(1) and two equivalent Co(1) atoms to form distorted ONa4Co2 octahedra that share corners with two equivalent O(2)Na4Co2 octahedra, corners with four equivalent O(1)Na2Co4 octahedra, edges with six equivalent O(1)Na2Co4 octahedra, and edges with six equivalent O(2)Na4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-18°.
NaCoO2 is Caswellsilverite-like structured and crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, edges with six equivalent Na(1)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°. There is one shorter (2.41 Å) and one longer (2.42 Å) Na(1)-O(1) bond length. There are a spread of Na(1)-O(2) bond distances ranging from 2.28-2.44 Å. Co(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with six equivalent Na(1)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. There is one shorter (1.81 Å) and one longer (2.17 Å) Co(1)-O(2) bond length. There are a spread of Co(1)-O(1) bond distances ranging from 1.91-2.27 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and four equivalent Co(1) atoms to form ONa2Co4 octahedra that share corners with two equivalent O(1)Na2Co4 octahedra, corners with four equivalent O(2)Na4Co2 octahedra, edges with six equivalent O(1)Na2Co4 octahedra, and edges with six equivalent O(2)Na4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second O site, O(2) is bonded to four equivalent Na(1) and two equivalent Co(1) atoms to form distorted ONa4Co2 octahedra that share corners with two equivalent O(2)Na4Co2 octahedra, corners with four equivalent O(1)Na2Co4 octahedra, edges with six equivalent O(1)Na2Co4 octahedra, and edges with six equivalent O(2)Na4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-18°.