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Rb2Se is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Rb1+ is bonded to four equivalent Se2- atoms to form a mixture of edge and corner-sharing RbSe4 tetrahedra. All Rb–Se bond lengths are 3.52 Å. Se2- is bonded in a body-centered cubic geometry to eight equivalent Rb1+ atoms.
Rb2Se5 crystallizes in the orthorhombic P2_12_12_1 space group. The structure is three-dimensional. there are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 10-coordinate geometry to ten Se+0.40- atoms. There are a spread of Rb–Se bond distances ranging from 3.49–3.85 Å. In the second Rb1+ site, Rb1+ is bonded in a 9-coordinate geometry to nine Se+0.40- atoms. There are a spread of Rb–Se bond distances ranging from 3.60–3.97 Å. There are five inequivalent Se+0.40- sites. In the first Se+0.40- site, Se+0.40- is bonded in a 7-coordinate geometry to six Rb1+ and one Se+0.40- atom. The Se–Se bond length is 2.36 Å. In the second Se+0.40- site, Se+0.40- is bonded in a 5-coordinate geometry to three Rb1+ and two Se+0.40- atoms. The Se–Se bond length is 2.40 Å. In the third Se+0.40- site, Se+0.40- is bonded in a 3-coordinate geometry to one Rb1+ and two Se+0.40- atoms. The Se–Se bond length is 2.42 Å. In the fourth Se+0.40- site, Se+0.40- is bonded in a 6-coordinate geometry to four Rb1+ and two Se+0.40- atoms. The Se–Se bond length is 2.37 Å. In the fifth Se+0.40- site, Se+0.40- is bonded in a 6-coordinate geometry to five Rb1+ and one Se+0.40- atom.
Rb2Se3 crystallizes in the orthorhombic Cmc2_1 space group. The structure is three-dimensional. there are two inequivalent Rb sites. In the first Rb site, Rb is bonded in a 7-coordinate geometry to seven Se atoms. There are a spread of Rb–Se bond distances ranging from 3.50–3.65 Å. In the second Rb site, Rb is bonded in a 8-coordinate geometry to eight Se atoms. There are a spread of Rb–Se bond distances ranging from 3.45–3.88 Å. There are two inequivalent Se sites. In the first Se site, Se is bonded to six Rb and one Se atom to form a mixture of distorted corner, edge, and face-sharing SeRb6Se pentagonal bipyramids. The Se–Se bond length is 2.42 Å. In the second Se site, Se is bonded in a 5-coordinate geometry to three Rb and two equivalent Se atoms.
RbSe is alpha boron-derived structured and crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. there are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 6-coordinate geometry to six Se1- atoms. There are four shorter (3.47 Å) and two longer (3.54 Å) Rb–Se bond lengths. In the second Rb1+ site, Rb1+ is bonded in a 6-coordinate geometry to six Se1- atoms. There are two shorter (3.54 Å) and four longer (3.63 Å) Rb–Se bond lengths. There are two inequivalent Se1- sites. In the first Se1- site, Se1- is bonded in a 7-coordinate geometry to six Rb1+ and one Se1- atom. The Se–Se bond length is 2.43 Å. In the second Se1- site, Se1- is bonded in a 7-coordinate geometry to six Rb1+ and one Se1- atom. The Se–Se bond length is 2.44 Å.