Rb8SnO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted RbO4 tetrahedra that share corners with two equivalent Sn(1)O4 tetrahedra, corners with four equivalent Rb(2)O4 tetrahedra, corners with six equivalent Rb(1)O4 tetrahedra, edges with two equivalent Rb(3)O4 tetrahedra, and edges with three equivalent Rb(2)O4 tetrahedra. In the second Rb site, Rb(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted RbO4 tetrahedra that share corners with four equivalent Rb(1)O4 tetrahedra, corners with four equivalent Rb(3)O4 tetrahedra, corners with six equivalent Rb(2)O4 tetrahedra,  an edgeedge with one Sn(1)O4 tetrahedra, and edges with three equivalent Rb(1)O4 tetrahedra. In the third Rb site, Rb(3) is bonded to one O(2) and three equivalent O(1) atoms to form RbO4 tetrahedra that share corners with three equivalent Rb(3)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, corners with six equivalent Rb(2)O4 tetrahedra, and edges with three equivalent Rb(1)O4 tetrahedra. Sn(1) is bonded to one O(3) and three equivalent O(1) atoms to form SnO4 tetrahedra that share corners with six equivalent Rb(1)O4 tetrahedra, corners with six equivalent Rb(3)O4 tetrahedra, and edges with three equivalent Rb(2)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), one Rb(2), two equivalent Rb(3), and one Sn(1) atom to form distorted ORb4Sn trigonal bipyramids that share corners with two equivalent O(2)Rb7 pentagonal bipyramids, corners with six equivalent O(1)Rb4Sn trigonal bipyramids, and edges with two equivalent O(2)Rb7 pentagonal bipyramids. In the second O site, O(2) is bonded to one Rb(3), three equivalent Rb(1), and three equivalent Rb(2) atoms to form distorted ORb7 pentagonal bipyramids that share corners with three equivalent O(1)Rb4Sn trigonal bipyramids, edges with three equivalent O(2)Rb7 pentagonal bipyramids, and edges with three equivalent O(1)Rb4Sn trigonal bipyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Rb(1), three equivalent Rb(2), and one Sn(1) atom.
Rb8SnO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted RbO4 tetrahedra that share corners with two equivalent Sn(1)O4 tetrahedra, corners with four equivalent Rb(2)O4 tetrahedra, corners with six equivalent Rb(1)O4 tetrahedra, edges with two equivalent Rb(3)O4 tetrahedra, and edges with three equivalent Rb(2)O4 tetrahedra. The Rb(1)-O(1) bond length is 2.85 Å. The Rb(1)-O(3) bond length is 3.17 Å. Both Rb(1)-O(2) bond lengths are 2.81 Å. In the second Rb site, Rb(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted RbO4 tetrahedra that share corners with four equivalent Rb(1)O4 tetrahedra, corners with four equivalent Rb(3)O4 tetrahedra, corners with six equivalent Rb(2)O4 tetrahedra,  an edgeedge with one Sn(1)O4 tetrahedra, and edges with three equivalent Rb(1)O4 tetrahedra. The Rb(2)-O(1) bond length is 2.85 Å. The Rb(2)-O(3) bond length is 2.99 Å. Both Rb(2)-O(2) bond lengths are 2.88 Å. In the third Rb site, Rb(3) is bonded to one O(2) and three equivalent O(1) atoms to form RbO4 tetrahedra that share corners with three equivalent Rb(3)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, corners with six equivalent Rb(2)O4 tetrahedra, and edges with three equivalent Rb(1)O4 tetrahedra. The Rb(3)-O(2) bond length is 2.95 Å. All Rb(3)-O(1) bond lengths are 2.92 Å. Sn(1) is bonded to one O(3) and three equivalent O(1) atoms to form SnO4 tetrahedra that share corners with six equivalent Rb(1)O4 tetrahedra, corners with six equivalent Rb(3)O4 tetrahedra, and edges with three equivalent Rb(2)O4 tetrahedra. The Sn(1)-O(3) bond length is 2.04 Å. All Sn(1)-O(1) bond lengths are 2.01 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), one Rb(2), two equivalent Rb(3), and one Sn(1) atom to form distorted ORb4Sn trigonal bipyramids that share corners with two equivalent O(2)Rb7 pentagonal bipyramids, corners with six equivalent O(1)Rb4Sn trigonal bipyramids, and edges with two equivalent O(2)Rb7 pentagonal bipyramids. In the second O site, O(2) is bonded to one Rb(3), three equivalent Rb(1), and three equivalent Rb(2) atoms to form distorted ORb7 pentagonal bipyramids that share corners with three equivalent O(1)Rb4Sn trigonal bipyramids, edges with three equivalent O(2)Rb7 pentagonal bipyramids, and edges with three equivalent O(1)Rb4Sn trigonal bipyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Rb(1), three equivalent Rb(2), and one Sn(1) atom.