Rb5Tl3O crystallizes in the orthorhombic Cmcm space group. There are five inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a water-like geometry to two equivalent Tl(1) and two equivalent O(2) atoms. In the second Rb site, Rb(2) is bonded in a single-bond geometry to four equivalent Tl(2) and one O(1) atom. In the third Rb site, Rb(3) is bonded in a single-bond geometry to two equivalent Tl(2), two equivalent Tl(3), and one O(1) atom. In the fourth Rb site, Rb(4) is bonded in a single-bond geometry to four equivalent Tl(3) and one O(2) atom. In the fifth Rb site, Rb(5) is bonded in a single-bond geometry to two equivalent Tl(1) and one O(1) atom. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted body-centered cubic geometry to two equivalent Rb(1), two equivalent Rb(5), two equivalent Tl(2), and two equivalent Tl(3) atoms. In the second Tl site, Tl(2) is bonded in a 8-coordinate geometry to two equivalent Rb(3), four equivalent Rb(2), and two equivalent Tl(1) atoms. In the third Tl site, Tl(3) is bonded in a 8-coordinate geometry to two equivalent Rb(3), four equivalent Rb(4), and two equivalent Tl(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in an octahedral geometry to two equivalent Rb(2), two equivalent Rb(3), and two equivalent Rb(5) atoms. In the second O site, O(2) is bonded to two equivalent Rb(4) and four equivalent Rb(1) atoms to form edge-sharing ORb6 octahedra.
Rb5Tl3O crystallizes in the orthorhombic Cmcm space group. There are five inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a water-like geometry to two equivalent Tl(1) and two equivalent O(2) atoms. Both Rb(1)-Tl(1) bond lengths are 4.23 Å. There is one shorter (2.99 Å) and one longer (3.05 Å) Rb(1)-O(2) bond length. In the second Rb site, Rb(2) is bonded in a single-bond geometry to four equivalent Tl(2) and one O(1) atom. There are two shorter (3.92 Å) and two longer (4.20 Å) Rb(2)-Tl(2) bond lengths. The Rb(2)-O(1) bond length is 2.86 Å. In the third Rb site, Rb(3) is bonded in a single-bond geometry to two equivalent Tl(2), two equivalent Tl(3), and one O(1) atom. Both Rb(3)-Tl(2) bond lengths are 4.19 Å. Both Rb(3)-Tl(3) bond lengths are 3.92 Å. The Rb(3)-O(1) bond length is 2.81 Å. In the fourth Rb site, Rb(4) is bonded in a single-bond geometry to four equivalent Tl(3) and one O(2) atom. There are two shorter (3.94 Å) and two longer (4.15 Å) Rb(4)-Tl(3) bond lengths. The Rb(4)-O(2) bond length is 2.67 Å. In the fifth Rb site, Rb(5) is bonded in a single-bond geometry to two equivalent Tl(1) and one O(1) atom. Both Rb(5)-Tl(1) bond lengths are 3.79 Å. The Rb(5)-O(1) bond length is 2.68 Å. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted body-centered cubic geometry to two equivalent Rb(1), two equivalent Rb(5), two equivalent Tl(2), and two equivalent Tl(3) atoms. Both Tl(1)-Tl(2) bond lengths are 3.20 Å. Both Tl(1)-Tl(3) bond lengths are 3.13 Å. In the second Tl site, Tl(2) is bonded in a 8-coordinate geometry to two equivalent Rb(3), four equivalent Rb(2), and two equivalent Tl(1) atoms. In the third Tl site, Tl(3) is bonded in a 8-coordinate geometry to two equivalent Rb(3), four equivalent Rb(4), and two equivalent Tl(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in an octahedral geometry to two equivalent Rb(2), two equivalent Rb(3), and two equivalent Rb(5) atoms. In the second O site, O(2) is bonded to two equivalent Rb(4) and four equivalent Rb(1) atoms to form edge-sharing ORb6 octahedra.