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NaCo3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Na is bonded in a 12-coordinate geometry to twelve equivalent Co atoms. There are six shorter (2.91 Å) and six longer (3.03 Å) Na–Co bond lengths. Co is bonded in a 10-coordinate geometry to four equivalent Na and six equivalent Co atoms. There are two shorter (2.37 Å) and four longer (2.43 Å) Co–Co bond lengths.
Na3Co is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. there are two inequivalent Na sites. In the first Na site, Na is bonded to four equivalent Na and four equivalent Co atoms to form a mixture of distorted corner, edge, and face-sharing NaNa4Co4 tetrahedra. All Na–Na bond lengths are 3.17 Å. All Na–Co bond lengths are 3.17 Å. In the second Na site, Na is bonded in a 8-coordinate geometry to eight equivalent Na and six equivalent Co atoms. All Na–Co bond lengths are 3.67 Å. Co is bonded in a body-centered cubic geometry to fourteen Na atoms.