RbLi3S2O9 crystallizes in the triclinic P1 space group. Rb(1) is bonded in a 8-coordinate geometry to one O(6), one O(8), two equivalent O(3), two equivalent O(5), and two equivalent O(9) atoms. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, and corners with two equivalent S(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(6), one O(7), one O(8), and one O(9) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, and corners with two equivalent S(2)O4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. In the second S site, S(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one S(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to two equivalent Rb(1), one Li(1), and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Rb(1), one Li(3), and one S(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Rb(1), one Li(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one S(1) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Rb(1), one Li(2), and one S(1) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to two equivalent Rb(1) and one Li(2) atom.
RbLi3S2O9 crystallizes in the triclinic P1 space group. Rb(1) is bonded in a 8-coordinate geometry to one O(6), one O(8), two equivalent O(3), two equivalent O(5), and two equivalent O(9) atoms. The Rb(1)-O(6) bond length is 3.07 Å. The Rb(1)-O(8) bond length is 3.11 Å. There is one shorter (3.02 Å) and one longer (3.25 Å) Rb(1)-O(3) bond length. There is one shorter (2.97 Å) and one longer (3.35 Å) Rb(1)-O(5) bond length. There is one shorter (3.36 Å) and one longer (3.38 Å) Rb(1)-O(9) bond length. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, and corners with two equivalent S(2)O4 tetrahedra. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(4) bond length is 1.97 Å. In the second Li site, Li(2) is bonded to one O(6), one O(7), one O(8), and one O(9) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Li(2)-O(6) bond length is 1.93 Å. The Li(2)-O(7) bond length is 1.98 Å. The Li(2)-O(8) bond length is 1.97 Å. The Li(2)-O(9) bond length is 2.04 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, and corners with two equivalent S(2)O4 tetrahedra. The Li(3)-O(1) bond length is 1.98 Å. The Li(3)-O(2) bond length is 1.99 Å. The Li(3)-O(5) bond length is 1.94 Å. The Li(3)-O(7) bond length is 1.97 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. The S(1)-O(2) bond length is 1.50 Å. The S(1)-O(4) bond length is 1.49 Å. The S(1)-O(7) bond length is 1.49 Å. The S(1)-O(8) bond length is 1.48 Å. In the second S site, S(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. The S(2)-O(1) bond length is 1.50 Å. The S(2)-O(3) bond length is 1.49 Å. The S(2)-O(5) bond length is 1.49 Å. The S(2)-O(6) bond length is 1.49 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one S(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to two equivalent Rb(1), one Li(1), and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Rb(1), one Li(3), and one S(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Rb(1), one Li(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one S(1) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Rb(1), one Li(2), and one S(1) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to two equivalent Rb(1) and one Li(2) atom.