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Cs2HgSe crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Cs2HgSe ribbons oriented in the (0, 1, 0) direction. Cs is bonded in a linear geometry to one Hg and one Se atom. The Cs–Hg bond length is 4.11 Å. The Cs–Se bond length is 3.07 Å. Hg is bonded in a linear geometry to two equivalent Cs atoms. Se is bonded in a linear geometry to two equivalent Cs atoms.
Cs2Hg3Se4 crystallizes in the orthorhombic Ibam space group. The structure is three-dimensional. Cs1+ is bonded in a body-centered cubic geometry to eight equivalent Se2- atoms. There are a spread of Cs–Se bond distances ranging from 3.75–4.05 Å. There are two inequivalent Hg2+ sites. In the first Hg2+ site, Hg2+ is bonded to four equivalent Se2- atoms to form a mixture of edge and corner-sharing HgSe4 tetrahedra. All Hg–Se bond lengths are 2.75 Å. In the second Hg2+ site, Hg2+ is bonded to four equivalent Se2- atoms to form a mixture of distorted edge and corner-sharing HgSe4 trigonal pyramids. There are two shorter (2.52 Å) and two longer (3.32 Å) Hg–Se bond lengths. Se2- is bonded in a 2-coordinate geometry to four equivalent Cs1+ and three Hg2+ atoms.