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MgRh is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Mg is bonded in a body-centered cubic geometry to eight equivalent Rh atoms. All Mg–Rh bond lengths are 2.71 Å. Rh is bonded in a body-centered cubic geometry to eight equivalent Mg atoms.
Mg5Rh2 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are three inequivalent Mg sites. In the first Mg site, Mg is bonded in a 12-coordinate geometry to six equivalent Rh atoms. All Mg–Rh bond lengths are 2.72 Å. In the second Mg site, Mg is bonded in a 3-coordinate geometry to three Rh atoms. There are two shorter (2.75 Å) and one longer (3.08 Å) Mg–Rh bond lengths. In the third Mg site, Mg is bonded in a 2-coordinate geometry to four Rh atoms. There are a spread of Mg–Rh bond distances ranging from 2.60–2.93 Å. There are two inequivalent Rh sites. In the first Rh site, Rh is bonded in a 6-coordinate geometry to nine Mg atoms. In the second Rh site, Rh is bonded in a 10-coordinate geometry to ten Mg atoms.