Rb5Au3O2 crystallizes in the orthorhombic Pbam space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 2-coordinate geometry to four equivalent Au(1) and two equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded in a distorted linear geometry to four equivalent Au(1) and two equivalent O(1) atoms. In the third Rb site, Rb(3) is bonded in a 2-coordinate geometry to four equivalent Au(1) and two equivalent O(1) atoms. There are two inequivalent Au sites. In the first Au site, Au(1) is bonded in a 10-coordinate geometry to two equivalent Rb(2), four equivalent Rb(1), and four equivalent Rb(3) atoms. In the second Au site, Au(2) is bonded in a linear geometry to two equivalent O(1) atoms. O(1) is bonded to one Rb(2), two equivalent Rb(1), two equivalent Rb(3), and one Au(2) atom to form corner-sharing ORb5Au octahedra. The corner-sharing octahedral tilt angles range from 0-15°.
Rb5Au3O2 crystallizes in the orthorhombic Pbam space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 2-coordinate geometry to four equivalent Au(1) and two equivalent O(1) atoms. There are a spread of Rb(1)-Au(1) bond distances ranging from 3.56-3.91 Å. Both Rb(1)-O(1) bond lengths are 2.84 Å. In the second Rb site, Rb(2) is bonded in a distorted linear geometry to four equivalent Au(1) and two equivalent O(1) atoms. All Rb(2)-Au(1) bond lengths are 3.68 Å. Both Rb(2)-O(1) bond lengths are 2.86 Å. In the third Rb site, Rb(3) is bonded in a 2-coordinate geometry to four equivalent Au(1) and two equivalent O(1) atoms. There are two shorter (3.59 Å) and two longer (3.84 Å) Rb(3)-Au(1) bond lengths. There is one shorter (2.72 Å) and one longer (2.80 Å) Rb(3)-O(1) bond length. There are two inequivalent Au sites. In the first Au site, Au(1) is bonded in a 10-coordinate geometry to two equivalent Rb(2), four equivalent Rb(1), and four equivalent Rb(3) atoms. In the second Au site, Au(2) is bonded in a linear geometry to two equivalent O(1) atoms. Both Au(2)-O(1) bond lengths are 2.02 Å. O(1) is bonded to one Rb(2), two equivalent Rb(1), two equivalent Rb(3), and one Au(2) atom to form corner-sharing ORb5Au octahedra. The corner-sharing octahedral tilt angles range from 0-15°.