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MgRh2Sb crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two MgRh2Sb ribbons oriented in the (1, 0, 0) direction. Mg is bonded in a linear geometry to two equivalent Rh atoms. Both Mg–Rh bond lengths are 2.67 Å. Rh is bonded in a linear geometry to one Mg and one Sb atom. The Rh–Sb bond length is 2.38 Å. Sb is bonded in a linear geometry to two equivalent Rh atoms.
MgRh2Sb is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Mg is bonded in a body-centered cubic geometry to eight equivalent Rh and six equivalent Sb atoms. All Mg–Rh bond lengths are 2.76 Å. All Mg–Sb bond lengths are 3.19 Å. Rh is bonded in a body-centered cubic geometry to four equivalent Mg and four equivalent Sb atoms. All Rh–Sb bond lengths are 2.76 Å. Sb is bonded in a distorted body-centered cubic geometry to six equivalent Mg and eight equivalent Rh atoms.