Rb4SnO4 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 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted RbO4 trigonal pyramids that share corners with four equivalent Sn(1)O4 tetrahedra, corners with two equivalent Rb(3)O5 trigonal bipyramids, and edges with two equivalent Rb(2)O4 trigonal pyramids. In the third Rb site, Rb(3) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted RbO5 trigonal bipyramids that share corners with three equivalent Sn(1)O4 tetrahedra, corners with two equivalent Rb(2)O4 trigonal pyramids,  an edgeedge with one Sn(1)O4 tetrahedra, and edges with two equivalent Rb(3)O5 trigonal bipyramids. In the fourth Rb site, Rb(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms. Sn(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SnO4 tetrahedra that share corners with three equivalent Rb(3)O5 trigonal bipyramids, corners with four equivalent Rb(2)O4 trigonal pyramids, and  an edgeedge with one Rb(3)O5 trigonal bipyramid. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Rb(4), two equivalent Rb(1), two equivalent Rb(2), and one Sn(1) atom. In the second O site, O(2) is bonded to one Rb(1), two equivalent Rb(3), two equivalent Rb(4), and one Sn(1) atom to form distorted edge-sharing ORb5Sn octahedra. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), one Rb(4), two equivalent Rb(2), and one Sn(1) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Rb(1), two equivalent Rb(3), two equivalent Rb(4), and one Sn(1) atom.
Rb4SnO4 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 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. The Rb(1)-O(2) bond length is 2.88 Å. The Rb(1)-O(3) bond length is 2.98 Å. The Rb(1)-O(4) bond length is 2.94 Å. There is one shorter (2.84 Å) and one longer (3.22 Å) Rb(1)-O(1) bond length. In the second Rb site, Rb(2) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted RbO4 trigonal pyramids that share corners with four equivalent Sn(1)O4 tetrahedra, corners with two equivalent Rb(3)O5 trigonal bipyramids, and edges with two equivalent Rb(2)O4 trigonal pyramids. There is one shorter (2.78 Å) and one longer (2.80 Å) Rb(2)-O(1) bond length. There is one shorter (2.78 Å) and one longer (2.79 Å) Rb(2)-O(3) bond length. In the third Rb site, Rb(3) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted RbO5 trigonal bipyramids that share corners with three equivalent Sn(1)O4 tetrahedra, corners with two equivalent Rb(2)O4 trigonal pyramids,  an edgeedge with one Sn(1)O4 tetrahedra, and edges with two equivalent Rb(3)O5 trigonal bipyramids. The Rb(3)-O(3) bond length is 3.00 Å. There is one shorter (2.75 Å) and one longer (2.83 Å) Rb(3)-O(2) bond length. There is one shorter (2.86 Å) and one longer (2.91 Å) Rb(3)-O(4) bond length. In the fourth Rb site, Rb(4) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms. The Rb(4)-O(1) bond length is 3.47 Å. The Rb(4)-O(3) bond length is 2.88 Å. There is one shorter (2.87 Å) and one longer (2.93 Å) Rb(4)-O(2) bond length. There is one shorter (3.05 Å) and one longer (3.07 Å) Rb(4)-O(4) bond length. Sn(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SnO4 tetrahedra that share corners with three equivalent Rb(3)O5 trigonal bipyramids, corners with four equivalent Rb(2)O4 trigonal pyramids, and  an edgeedge with one Rb(3)O5 trigonal bipyramid. The Sn(1)-O(1) bond length is 1.97 Å. The Sn(1)-O(2) bond length is 1.99 Å. The Sn(1)-O(3) bond length is 1.98 Å. The Sn(1)-O(4) bond length is 1.99 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Rb(4), two equivalent Rb(1), two equivalent Rb(2), and one Sn(1) atom. In the second O site, O(2) is bonded to one Rb(1), two equivalent Rb(3), two equivalent Rb(4), and one Sn(1) atom to form distorted edge-sharing ORb5Sn octahedra. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), one Rb(4), two equivalent Rb(2), and one Sn(1) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Rb(1), two equivalent Rb(3), two equivalent Rb(4), and one Sn(1) atom.