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LiScRh2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiScRh2 ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to two equivalent Rh atoms. Both Li–Rh bond lengths are 2.55 Å. Sc is bonded in a linear geometry to two equivalent Rh atoms. Both Sc–Rh bond lengths are 2.19 Å. Rh is bonded in a linear geometry to one Li and one Sc atom.
LiScRh2 is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Li is bonded in a body-centered cubic geometry to eight equivalent Rh atoms. All Li–Rh bond lengths are 2.69 Å. Sc is bonded in a body-centered cubic geometry to eight equivalent Rh atoms. All Sc–Rh bond lengths are 2.69 Å. Rh is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Sc atoms.