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PrRh2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Pr is bonded in a 12-coordinate geometry to twelve equivalent Rh atoms. All Pr–Rh bond lengths are 3.19 Å. Rh is bonded to six equivalent Pr and six equivalent Rh atoms to form a mixture of edge, face, and corner-sharing RhPr6Rh6 cuboctahedra. All Rh–Rh bond lengths are 2.72 Å.
PrRh crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. Pr is bonded in a 7-coordinate geometry to seven equivalent Rh atoms. There are a spread of Pr–Rh bond distances ranging from 3.00–3.19 Å. Rh is bonded in a 9-coordinate geometry to seven equivalent Pr and two equivalent Rh atoms. Both Rh–Rh bond lengths are 2.86 Å.
Pr3Rh2 crystallizes in the trigonal R-3 space group. The structure is three-dimensional. there are three inequivalent Pr sites. In the first Pr site, Pr is bonded in an octahedral geometry to six equivalent Rh atoms. All Pr–Rh bond lengths are 3.08 Å. In the second Pr site, Pr is bonded in a 6-coordinate geometry to six equivalent Rh atoms. There are three shorter (2.94 Å) and three longer (3.17 Å) Pr–Rh bond lengths. In the third Pr site, Pr is bonded in a 5-coordinate geometry to five equivalent Rh atoms. There are a spread of Pr–Rh bond distances ranging from 2.93–3.34 Å. Rh is bonded in a 8-coordinate geometry to eight Pr atoms.