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Rb2HgSe crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Rb2HgSe ribbons oriented in the (0, 1, 0) direction. Rb is bonded in a linear geometry to one Hg and one Se atom. The Rb–Hg bond length is 3.95 Å. The Rb–Se bond length is 2.96 Å. Hg is bonded in a linear geometry to two equivalent Rb atoms. Se is bonded in a linear geometry to two equivalent Rb atoms.
Rb2Hg3Se4 crystallizes in the orthorhombic Ibam space group. The structure is three-dimensional. Rb1+ is bonded in a body-centered cubic geometry to eight equivalent Se2- atoms. There are a spread of Rb–Se bond distances ranging from 3.60–3.94 Å. There are two inequivalent Hg2+ sites. In the first Hg2+ site, Hg2+ is bonded in a tetrahedral geometry to four equivalent Se2- atoms. All Hg–Se bond lengths are 2.75 Å. In the second Hg2+ site, Hg2+ is bonded in a distorted rectangular see-saw-like geometry to four equivalent Se2- atoms. There are two shorter (2.53 Å) and two longer (3.33 Å) Hg–Se bond lengths. Se2- is bonded in a 2-coordinate geometry to four equivalent Rb1+ and three Hg2+ atoms.
Rb6HgSe4 crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. there are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded to four Se2- atoms to form distorted RbSe4 tetrahedra that share corners with two equivalent HgSe4 tetrahedra, corners with eight equivalent RbSe4 tetrahedra, and an edgeedge with one HgSe4 tetrahedra. There are three shorter (3.42 Å) and one longer (3.50 Å) Rb–Se bond lengths. In the second Rb1+ site, Rb1+ is bonded in a 5-coordinate geometry to five Se2- atoms. There are a spread of Rb–Se bond distances ranging from 3.52–3.77 Å. Hg2+ is bonded to four Se2- atoms to form HgSe4 tetrahedra that share corners with six equivalent RbSe4 tetrahedra and edges with three equivalent RbSe4 tetrahedra. There are three shorter (2.78 Å) and one longer (2.81 Å) Hg–Se bond lengths. There are two inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a 7-coordinate geometry to six Rb1+ and one Hg2+ atom. In the second Se2- site, Se2- is bonded in a 8-coordinate geometry to seven Rb1+ and one Hg2+ atom.