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Li2PbSn crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Li2PbSn ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to one Pb and one Sn atom. The Li–Pb bond length is 2.83 Å. The Li–Sn bond length is 2.78 Å. Pb is bonded in a linear geometry to two equivalent Li atoms. Sn is bonded in a linear geometry to two equivalent Li atoms.
Li2PbSn 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 Pb and four equivalent Sn atoms. All Li–Pb bond lengths are 3.05 Å. All Li–Sn bond lengths are 3.05 Å. Pb is bonded in a body-centered cubic geometry to eight equivalent Li atoms. Sn is bonded in a body-centered cubic geometry to eight equivalent Li atoms.