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Bi2Rb is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Rb is bonded in a 12-coordinate geometry to twelve equivalent Bi atoms. All Rb–Bi bond lengths are 4.03 Å. Bi is bonded to six equivalent Rb and six equivalent Bi atoms to form a mixture of corner, edge, and face-sharing BiRb6Bi6 cuboctahedra. All Bi–Bi bond lengths are 3.43 Å.
Rb3Bi is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. there are two inequivalent Rb sites. In the first Rb site, Rb is bonded to four equivalent Rb and four equivalent Bi atoms to form a mixture of distorted edge, face, and corner-sharing RbRb4Bi4 tetrahedra. All Rb–Rb bond lengths are 3.96 Å. All Rb–Bi bond lengths are 3.96 Å. In the second Rb site, Rb is bonded in a body-centered cubic geometry to eight equivalent Rb atoms. Bi is bonded in a body-centered cubic geometry to eight equivalent Rb atoms.
Rb3Bi is Sodium arsenide structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Rb sites. In the first Rb site, Rb is bonded in a 1-coordinate geometry to four equivalent Bi atoms. There are one shorter (3.84 Å) and three longer (4.25 Å) Rb–Bi bond lengths. In the second Rb site, Rb is bonded in a trigonal planar geometry to three equivalent Bi atoms. All Rb–Bi bond lengths are 3.78 Å. Bi is bonded in a 5-coordinate geometry to eleven Rb atoms.