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Rb2O crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three Rb2O sheets oriented in the (0, 0, 1) direction. Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three equivalent O2- atoms. All Rb–O bond lengths are 2.80 Å. O2- is bonded to six equivalent Rb1+ atoms to form distorted edge-sharing ORb6 octahedra.
Rb2O is trigonal omega structured and crystallizes in the triclinic P1 space group. The structure is two-dimensional and consists of one Rb2O sheet oriented in the (1, 0, 0) direction. there are six inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Rb–O bond distances ranging from 2.78–2.82 Å. In the second Rb1+ site, Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Rb–O bond distances ranging from 2.78–2.82 Å. In the third Rb1+ site, Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Rb–O bond distances ranging from 2.78–2.82 Å. In the fourth Rb1+ site, Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Rb–O bond distances ranging from 2.78–2.81 Å. In the fifth Rb1+ site, Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Rb–O bond distances ranging from 2.78–2.82 Å. In the sixth Rb1+ site, Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three O2- atoms. There are a spread of Rb–O bond distances ranging from 2.78–2.81 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded to six Rb1+ atoms to form edge-sharing ORb6 octahedra. In the second O2- site, O2- is bonded to six Rb1+ atoms to form edge-sharing ORb6 octahedra. In the third O2- site, O2- is bonded to six Rb1+ atoms to form edge-sharing ORb6 octahedra.
Rb2O is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Rb1+ is bonded to four equivalent O2- atoms to form a mixture of edge and corner-sharing RbO4 tetrahedra. All Rb–O bond lengths are 2.98 Å. O2- is bonded in a body-centered cubic geometry to eight equivalent Rb1+ atoms.
Rb2O is Hydrophilite-like structured and crystallizes in the monoclinic P2_1 space group. The structure is three-dimensional. there are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a trigonal planar geometry to three equivalent O2- atoms. There are a spread of Rb–O bond distances ranging from 2.81–2.90 Å. In the second Rb1+ site, Rb1+ is bonded in a trigonal planar geometry to three equivalent O2- atoms. There are two shorter (2.81 Å) and one longer (2.92 Å) Rb–O bond lengths. O2- is bonded to six Rb1+ atoms to form a mixture of edge and corner-sharing ORb6 octahedra. The corner-sharing octahedra tilt angles range from 51–56°.
Rb2O is Cotunnite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a distorted trigonal non-coplanar geometry to three equivalent O2- atoms. There are one shorter (2.75 Å) and two longer (3.05 Å) Rb–O bond lengths. In the second Rb1+ site, Rb1+ is bonded to four equivalent O2- atoms to form a mixture of edge and corner-sharing RbO4 tetrahedra. There are a spread of Rb–O bond distances ranging from 2.87–2.99 Å. O2- is bonded in a 7-coordinate geometry to seven Rb1+ atoms.