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LiMgHg2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiMgHg2 ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to two equivalent Hg atoms. Both Li–Hg bond lengths are 2.75 Å. Mg is bonded in a linear geometry to two equivalent Hg atoms. Both Mg–Hg bond lengths are 2.99 Å. Hg is bonded in a linear geometry to one Li and one Mg atom.
LiMgHg2 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 Hg atoms. All Li–Hg bond lengths are 2.97 Å. Mg is bonded in a body-centered cubic geometry to eight equivalent Hg atoms. All Mg–Hg bond lengths are 2.97 Å. Hg is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Mg atoms.