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SmSn3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Sm is bonded to twelve equivalent Sn atoms to form a mixture of face and corner-sharing SmSn12 cuboctahedra. All Sm–Sn bond lengths are 3.36 Å. Sn is bonded in a distorted square co-planar geometry to four equivalent Sm atoms.
Sm5Sn3 crystallizes in the hexagonal P6_3/mcm space group. The structure is three-dimensional. there are two inequivalent Sm sites. In the first Sm site, Sm is bonded in a 6-coordinate geometry to six equivalent Sn atoms. All Sm–Sn bond lengths are 3.29 Å. In the second Sm site, Sm is bonded in a 5-coordinate geometry to five equivalent Sn atoms. There are a spread of Sm–Sn bond distances ranging from 3.16–3.66 Å. Sn is bonded in a 9-coordinate geometry to nine Sm atoms.