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Bi2Cs is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Cs is bonded in a 12-coordinate geometry to twelve equivalent Bi atoms. All Cs–Bi bond lengths are 4.08 Å. Bi is bonded to six equivalent Cs and six equivalent Bi atoms to form a mixture of corner, edge, and face-sharing BiCs6Bi6 cuboctahedra. All Bi–Bi bond lengths are 3.48 Å.
BiCs3 is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. there are two inequivalent Cs sites. In the first Cs site, Cs is bonded to four equivalent Cs and four equivalent Bi atoms to form a mixture of distorted edge, corner, and face-sharing CsCs4Bi4 tetrahedra. All Cs–Cs bond lengths are 4.13 Å. All Cs–Bi bond lengths are 4.13 Å. In the second Cs site, Cs is bonded in a body-centered cubic geometry to eight equivalent Cs atoms. Bi is bonded in a body-centered cubic geometry to eight equivalent Cs atoms.
Bi2Cs3 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. there are two inequivalent Cs sites. In the first Cs site, Cs is bonded in a 6-coordinate geometry to six equivalent Bi atoms. There are a spread of Cs–Bi bond distances ranging from 4.15–4.27 Å. In the second Cs site, Cs is bonded in a 6-coordinate geometry to six equivalent Bi atoms. There are a spread of Cs–Bi bond distances ranging from 3.95–4.30 Å. Bi is bonded in a 10-coordinate geometry to nine Cs and one Bi atom. The Bi–Bi bond length is 2.99 Å.
CsBi is Magnesium tetraboride-like structured and crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are four inequivalent Cs sites. In the first Cs site, Cs is bonded in a 6-coordinate geometry to six Bi atoms. There are a spread of Cs–Bi bond distances ranging from 3.90–4.32 Å. In the second Cs site, Cs is bonded in a 7-coordinate geometry to seven Bi atoms. There are a spread of Cs–Bi bond distances ranging from 3.92–4.59 Å. In the third Cs site, Cs is bonded in a 7-coordinate geometry to seven Bi atoms. There are a spread of Cs–Bi bond distances ranging from 3.92–4.41 Å. In the fourth Cs site, Cs is bonded in a 6-coordinate geometry to six Bi atoms. There are a spread of Cs–Bi bond distances ranging from 3.88–4.33 Å. There are four inequivalent Bi sites. In the first Bi site, Bi is bonded in a 8-coordinate geometry to six Cs and two equivalent Bi atoms. There are one shorter (3.06 Å) and one longer (3.08 Å) Bi–Bi bond lengths. In the second Bi site, Bi is bonded in a 9-coordinate geometry to seven Cs and two equivalent Bi atoms. In the third Bi site, Bi is bonded in a 8-coordinate geometry to six Cs and two equivalent Bi atoms. There are one shorter (3.07 Å) and one longer (3.09 Å) Bi–Bi bond lengths. In the fourth Bi site, Bi is bonded in a 9-coordinate geometry to seven Cs and two equivalent Bi atoms.