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Li2CdBi crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Li2CdBi ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to one Cd and one Bi atom. The Li–Cd bond length is 2.91 Å. The Li–Bi bond length is 2.74 Å. Cd is bonded in a linear geometry to two equivalent Li atoms. Bi is bonded in a linear geometry to two equivalent Li atoms.
Li2CdBi 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 four equivalent Cd and four equivalent Bi atoms. All Li–Cd bond lengths are 3.01 Å. All Li–Bi bond lengths are 3.01 Å. Cd is bonded in a body-centered cubic geometry to eight equivalent Li atoms. Bi is bonded in a body-centered cubic geometry to eight equivalent Li atoms.