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CaHg2 crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one CaHg2 sheet oriented in the (0, 0, 1) direction. Ca is bonded in a hexagonal planar geometry to six equivalent Hg atoms. All Ca–Hg bond lengths are 3.13 Å. Hg is bonded in a distorted trigonal planar geometry to three equivalent Ca atoms.
CaHg2 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Ca is bonded to twelve equivalent Hg atoms to form a mixture of edge and face-sharing CaHg12 cuboctahedra. All Ca–Hg bond lengths are 3.42 Å. Hg is bonded in a 9-coordinate geometry to six equivalent Ca and three equivalent Hg atoms. All Hg–Hg bond lengths are 2.90 Å.