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KBi2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. K is bonded in a 12-coordinate geometry to twelve equivalent Bi atoms. All K–Bi bond lengths are 3.98 Å. Bi is bonded to six equivalent K and six equivalent Bi atoms to form a mixture of face, edge, and corner-sharing BiK6Bi6 cuboctahedra. All Bi–Bi bond lengths are 3.40 Å.
K3Bi is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. there are two inequivalent K sites. In the first K site, K is bonded to four equivalent K and four equivalent Bi atoms to form a mixture of distorted edge, face, and corner-sharing KK4Bi4 tetrahedra. All K–K bond lengths are 3.78 Å. All K–Bi bond lengths are 3.78 Å. In the second K site, K is bonded in a body-centered cubic geometry to eight equivalent K atoms. Bi is bonded in a body-centered cubic geometry to eight equivalent K atoms.
K3Bi is Sodium arsenide structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent K sites. In the first K site, K is bonded in a 1-coordinate geometry to four equivalent Bi atoms. There are one shorter (3.68 Å) and three longer (4.06 Å) K–Bi bond lengths. In the second K site, K is bonded in a trigonal planar geometry to three equivalent Bi atoms. All K–Bi bond lengths are 3.61 Å. Bi is bonded in a 5-coordinate geometry to eleven K atoms.
K5Bi4 crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are five inequivalent K sites. In the first K site, K is bonded in a 6-coordinate geometry to six Bi atoms. There are a spread of K–Bi bond distances ranging from 3.83–3.88 Å. In the second K site, K is bonded in a 6-coordinate geometry to six Bi atoms. There are a spread of K–Bi bond distances ranging from 3.80–3.93 Å. In the third K site, K is bonded in a 7-coordinate geometry to seven Bi atoms. There are a spread of K–Bi bond distances ranging from 3.75–3.88 Å. In the fourth K site, K is bonded in a 7-coordinate geometry to seven Bi atoms. There are a spread of K–Bi bond distances ranging from 3.77–3.87 Å. In the fifth K site, K is bonded in a distorted square co-planar geometry to four Bi atoms. There are two shorter (3.61 Å) and two longer (3.64 Å) K–Bi bond lengths. There are four inequivalent Bi sites. In the first Bi site, Bi is bonded in a 9-coordinate geometry to eight K and one Bi atom. The Bi–Bi bond length is 3.01 Å. In the second Bi site, Bi is bonded in a 9-coordinate geometry to eight K and one Bi atom. The Bi–Bi bond length is 3.01 Å. In the third Bi site, Bi is bonded in a 9-coordinate geometry to seven K and two Bi atoms. The Bi–Bi bond length is 3.04 Å. In the fourth Bi site, Bi is bonded in a 9-coordinate geometry to seven K and two Bi atoms.
K5Bi4 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are three inequivalent K sites. In the first K site, K is bonded in a 7-coordinate geometry to seven Bi atoms. There are a spread of K–Bi bond distances ranging from 3.78–3.87 Å. In the second K site, K is bonded in a 6-coordinate geometry to six Bi atoms. There are a spread of K–Bi bond distances ranging from 3.81–3.88 Å. In the third K site, K is bonded in a distorted square co-planar geometry to four equivalent Bi atoms. All K–Bi bond lengths are 3.61 Å. There are two inequivalent Bi sites. In the first Bi site, Bi is bonded in a 9-coordinate geometry to seven K and two Bi atoms. There are one shorter (3.01 Å) and one longer (3.05 Å) Bi–Bi bond lengths. In the second Bi site, Bi is bonded in a 9-coordinate geometry to eight K and one Bi atom.