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RbSn3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Rb is bonded in a 12-coordinate geometry to twelve equivalent Sn atoms. There are six shorter (3.94 Å) and six longer (4.01 Å) Rb–Sn bond lengths. Sn is bonded in a 10-coordinate geometry to four equivalent Rb and six equivalent Sn atoms. There are two shorter (3.07 Å) and four longer (3.27 Å) Sn–Sn bond lengths.
Rb3Sn 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 Sn atoms to form a mixture of distorted edge, corner, and face-sharing RbRb4Sn4 tetrahedra. All Rb–Rb bond lengths are 4.03 Å. All Rb–Sn bond lengths are 4.03 Å. In the second Rb site, Rb is bonded in a body-centered cubic geometry to eight equivalent Rb atoms. Sn is bonded in a body-centered cubic geometry to eight equivalent Rb atoms.