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LiY2Hg crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiY2Hg ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to two equivalent Y atoms. Both Li–Y bond lengths are 3.16 Å. Y is bonded in a linear geometry to one Li and one Hg atom. The Y–Hg bond length is 2.98 Å. Hg is bonded in a linear geometry to two equivalent Y atoms.
LiY2Hg 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 Y atoms. All Li–Y bond lengths are 3.21 Å. Y is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Hg atoms. All Y–Hg bond lengths are 3.21 Å. Hg is bonded in a body-centered cubic geometry to eight equivalent Y atoms.