Rb4Sn(SeO)4 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 3-coordinate geometry to one Se(4), one O(2), one O(3), and one O(4) atom. In the second Rb site, Rb(2) is bonded in a 3-coordinate geometry to one O(2), one O(3), and one O(4) atom. In the third Rb site, Rb(3) is bonded in a 7-coordinate geometry to one Se(2), two equivalent Se(4), one O(3), one O(4), and two equivalent O(1) atoms. In the fourth Rb site, Rb(4) is bonded in a 8-coordinate geometry to two equivalent Se(2), two equivalent Se(4), one O(1), one O(2), one O(3), and one O(4) atom. Sn(1) is bonded to one Se(1), one Se(2), one Se(3), and one Se(4) atom to form SnSe4 tetrahedra that share  a cornercorner with one O(2)Rb3Se trigonal pyramid. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a 1-coordinate geometry to one Sn(1) and one O(1) atom. In the second Se site, Se(2) is bonded in a distorted single-bond geometry to one Rb(3), two equivalent Rb(4), one Sn(1), and one O(3) atom. In the third Se site, Se(3) is bonded in a distorted single-bond geometry to one Sn(1) and one O(2) atom. In the fourth Se site, Se(4) is bonded to one Rb(1), two equivalent Rb(3), two equivalent Rb(4), and one Sn(1) atom to form distorted SeRb5Sn pentagonal pyramids that share  a cornercorner with one O(2)Rb3Se trigonal pyramid, edges with two equivalent Se(4)Rb5Sn pentagonal pyramids, and  an edgeedge with one O(2)Rb3Se trigonal pyramid. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Rb(4), two equivalent Rb(3), one Se(1), and one O(4) atom. In the second O site, O(2) is bonded to one Rb(1), one Rb(2), one Rb(4), and one Se(3) atom to form distorted ORb3Se trigonal pyramids that share  a cornercorner with one Se(4)Rb5Sn pentagonal pyramid,  a cornercorner with one Sn(1)Se4 tetrahedra, and  an edgeedge with one Se(4)Rb5Sn pentagonal pyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), and one Se(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), and one O(1) atom.
Rb4Sn(SeO)4 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 3-coordinate geometry to one Se(4), one O(2), one O(3), and one O(4) atom. The Rb(1)-Se(4) bond length is 3.55 Å. The Rb(1)-O(2) bond length is 2.85 Å. The Rb(1)-O(3) bond length is 2.94 Å. The Rb(1)-O(4) bond length is 2.86 Å. In the second Rb site, Rb(2) is bonded in a 3-coordinate geometry to one O(2), one O(3), and one O(4) atom. The Rb(2)-O(2) bond length is 2.90 Å. The Rb(2)-O(3) bond length is 2.98 Å. The Rb(2)-O(4) bond length is 2.94 Å. In the third Rb site, Rb(3) is bonded in a 7-coordinate geometry to one Se(2), two equivalent Se(4), one O(3), one O(4), and two equivalent O(1) atoms. The Rb(3)-Se(2) bond length is 3.50 Å. There is one shorter (3.55 Å) and one longer (3.58 Å) Rb(3)-Se(4) bond length. The Rb(3)-O(3) bond length is 3.15 Å. The Rb(3)-O(4) bond length is 3.21 Å. There is one shorter (2.89 Å) and one longer (2.99 Å) Rb(3)-O(1) bond length. In the fourth Rb site, Rb(4) is bonded in a 8-coordinate geometry to two equivalent Se(2), two equivalent Se(4), one O(1), one O(2), one O(3), and one O(4) atom. There is one shorter (3.57 Å) and one longer (3.67 Å) Rb(4)-Se(2) bond length. There is one shorter (3.56 Å) and one longer (3.69 Å) Rb(4)-Se(4) bond length. The Rb(4)-O(1) bond length is 3.37 Å. The Rb(4)-O(2) bond length is 2.90 Å. The Rb(4)-O(3) bond length is 3.22 Å. The Rb(4)-O(4) bond length is 2.86 Å. Sn(1) is bonded to one Se(1), one Se(2), one Se(3), and one Se(4) atom to form SnSe4 tetrahedra that share  a cornercorner with one O(2)Rb3Se trigonal pyramid. The Sn(1)-Se(1) bond length is 2.61 Å. The Sn(1)-Se(2) bond length is 2.67 Å. The Sn(1)-Se(3) bond length is 2.71 Å. The Sn(1)-Se(4) bond length is 2.51 Å. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a 1-coordinate geometry to one Sn(1) and one O(1) atom. The Se(1)-O(1) bond length is 2.05 Å. In the second Se site, Se(2) is bonded in a distorted single-bond geometry to one Rb(3), two equivalent Rb(4), one Sn(1), and one O(3) atom. The Se(2)-O(3) bond length is 1.79 Å. In the third Se site, Se(3) is bonded in a distorted single-bond geometry to one Sn(1) and one O(2) atom. The Se(3)-O(2) bond length is 1.77 Å. In the fourth Se site, Se(4) is bonded to one Rb(1), two equivalent Rb(3), two equivalent Rb(4), and one Sn(1) atom to form distorted SeRb5Sn pentagonal pyramids that share  a cornercorner with one O(2)Rb3Se trigonal pyramid, edges with two equivalent Se(4)Rb5Sn pentagonal pyramids, and  an edgeedge with one O(2)Rb3Se trigonal pyramid. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Rb(4), two equivalent Rb(3), one Se(1), and one O(4) atom. The O(1)-O(4) bond length is 1.44 Å. In the second O site, O(2) is bonded to one Rb(1), one Rb(2), one Rb(4), and one Se(3) atom to form distorted ORb3Se trigonal pyramids that share  a cornercorner with one Se(4)Rb5Sn pentagonal pyramid,  a cornercorner with one Sn(1)Se4 tetrahedra, and  an edgeedge with one Se(4)Rb5Sn pentagonal pyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), and one Se(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), and one O(1) atom.