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Li2InBi crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Li2InBi ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to one In and one Bi atom. The Li–In bond length is 2.95 Å. The Li–Bi bond length is 2.77 Å. In is bonded in a linear geometry to two equivalent Li atoms. Bi is bonded in a linear geometry to two equivalent Li atoms.
Li2InBi 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 In and four equivalent Bi atoms. All Li–In bond lengths are 3.08 Å. All Li–Bi bond lengths are 3.08 Å. In 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.