Rb4Sn(Te2O)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted water-like geometry to one Sn(1), two equivalent Te(2), and two equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded in a distorted single-bond geometry to one Sn(1), three equivalent Te(2), and one O(1) atom. Sn(1) is bonded to two equivalent Rb(1), two equivalent Rb(2), two equivalent Te(1), and two equivalent Te(2) atoms to form distorted SnRb4Te4 tetrahedra that share corners with four equivalent O(1)Rb3Te tetrahedra and edges with two equivalent O(1)Rb3Te tetrahedra. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a single-bond geometry to one Sn(1) and one O(1) atom. In the second Te site, Te(2) is bonded in a 6-coordinate geometry to two equivalent Rb(1), three equivalent Rb(2), and one Sn(1) atom. O(1) is bonded to one Rb(2), two equivalent Rb(1), and one Te(1) atom to form distorted ORb3Te tetrahedra that share corners with two equivalent Sn(1)Rb4Te4 tetrahedra, corners with two equivalent O(1)Rb3Te tetrahedra, and  an edgeedge with one Sn(1)Rb4Te4 tetrahedra.
Rb4Sn(Te2O)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted water-like geometry to one Sn(1), two equivalent Te(2), and two equivalent O(1) atoms. The Rb(1)-Sn(1) bond length is 3.89 Å. There is one shorter (3.87 Å) and one longer (3.92 Å) Rb(1)-Te(2) bond length. There is one shorter (2.80 Å) and one longer (2.85 Å) Rb(1)-O(1) bond length. In the second Rb site, Rb(2) is bonded in a distorted single-bond geometry to one Sn(1), three equivalent Te(2), and one O(1) atom. The Rb(2)-Sn(1) bond length is 4.07 Å. There are a spread of Rb(2)-Te(2) bond distances ranging from 3.63-4.06 Å. The Rb(2)-O(1) bond length is 2.85 Å. Sn(1) is bonded to two equivalent Rb(1), two equivalent Rb(2), two equivalent Te(1), and two equivalent Te(2) atoms to form distorted SnRb4Te4 tetrahedra that share corners with four equivalent O(1)Rb3Te tetrahedra and edges with two equivalent O(1)Rb3Te tetrahedra. Both Sn(1)-Te(1) bond lengths are 2.88 Å. Both Sn(1)-Te(2) bond lengths are 2.76 Å. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a single-bond geometry to one Sn(1) and one O(1) atom. The Te(1)-O(1) bond length is 1.94 Å. In the second Te site, Te(2) is bonded in a 6-coordinate geometry to two equivalent Rb(1), three equivalent Rb(2), and one Sn(1) atom. O(1) is bonded to one Rb(2), two equivalent Rb(1), and one Te(1) atom to form distorted ORb3Te tetrahedra that share corners with two equivalent Sn(1)Rb4Te4 tetrahedra, corners with two equivalent O(1)Rb3Te tetrahedra, and  an edgeedge with one Sn(1)Rb4Te4 tetrahedra.