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MgVRh2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two MgVRh2 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 2.76 Å. V is bonded in a linear geometry to two equivalent Rh atoms. Both V–Rh bond lengths are 2.03 Å. Rh is bonded in a linear geometry to one Mg and one V atom.
MgVRh2 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 atoms. All Mg–Rh bond lengths are 2.65 Å. V is bonded in a body-centered cubic geometry to eight equivalent Rh atoms. All V–Rh bond lengths are 2.65 Å. Rh is bonded in a body-centered cubic geometry to four equivalent Mg and four equivalent V atoms.