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RhSn crystallizes in the cubic P2_13 space group. The structure is three-dimensional. Rh is bonded in a 7-coordinate geometry to seven equivalent Sn atoms. There are a spread of Rh–Sn bond distances ranging from 2.72–2.88 Å. Sn is bonded in a 7-coordinate geometry to seven equivalent Rh atoms.
Ce(RhSn)2 crystallizes in the tetragonal P4/nmm space group. The structure is three-dimensional. Ce is bonded in a 12-coordinate geometry to eight Rh and eight Sn atoms. There are four shorter (3.45 Å) and four longer (3.48 Å) Ce–Rh bond lengths. There are four shorter (3.44 Å) and four longer (3.53 Å) Ce–Sn bond lengths. There are two inequivalent Rh sites. In the first Rh site, Rh is bonded in a 4-coordinate geometry to four equivalent Ce and four equivalent Sn atoms. All Rh–Sn bond lengths are 2.64 Å. In the second Rh site, Rh is bonded in a 9-coordinate geometry to four equivalent Ce and five Sn atoms. There are one shorter (2.57 Å) and four longer (2.67 Å) Rh–Sn bond lengths. There are two inequivalent Sn sites. In the first Sn site, Sn is bonded to four equivalent Ce and four equivalent Rh atoms to form a mixture of distorted face and edge-sharing SnCe4Rh4 tetrahedra. In the second Sn site, Sn is bonded in a 9-coordinate geometry to four equivalent Ce and five Rh atoms.