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K3Co crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. K is bonded in a 12-coordinate geometry to eight equivalent K and four equivalent Co atoms. There are a spread of K–K bond distances ranging from 3.76–4.35 Å. There are two shorter (3.83 Å) and two longer (4.06 Å) K–Co bond lengths. Co is bonded to twelve equivalent K atoms to form a mixture of corner and face-sharing CoK12 cuboctahedra.
K3Co crystallizes in the monoclinic P2_1/c space group. The structure is one-dimensional and consists of two K3Co ribbons oriented in the (0, 0, 1) direction. there are two inequivalent K sites. In the first K site, K is bonded in a 2-coordinate geometry to two equivalent Co atoms. Both K–Co bond lengths are 4.10 Å. In the second K site, K is bonded in a 1-coordinate geometry to one Co atom. The K–Co bond length is 4.13 Å. Co is bonded in a square co-planar geometry to four K atoms.
K3Co is alpha bismuth trifluoride structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent K sites. In the first K site, K is bonded in a 12-coordinate geometry to four equivalent K and four equivalent Co atoms. All K–K bond lengths are 3.98 Å. All K–Co bond lengths are 3.98 Å. In the second K site, K is bonded to eight equivalent K and four equivalent Co atoms to form a mixture of distorted corner, edge, and face-sharing KK8Co4 cuboctahedra. All K–Co bond lengths are 4.18 Å. Co is bonded in a distorted body-centered cubic geometry to twelve K atoms.