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Ca2HgBi crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Ca2HgBi ribbons oriented in the (1, 0, 0) direction. Ca is bonded in a linear geometry to one Hg and one Bi atom. The Ca–Hg bond length is 3.27 Å. The Ca–Bi bond length is 2.84 Å. Hg is bonded in a linear geometry to two equivalent Ca atoms. Bi is bonded in a linear geometry to two equivalent Ca atoms.
Ca2HgBi is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ca is bonded in a body-centered cubic geometry to four equivalent Hg and four equivalent Bi atoms. All Ca–Hg bond lengths are 3.38 Å. All Ca–Bi bond lengths are 3.38 Å. Hg is bonded in a body-centered cubic geometry to eight equivalent Ca atoms. Bi is bonded in a body-centered cubic geometry to eight equivalent Ca atoms.