Tl3S2O9 crystallizes in the monoclinic Cc space group. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom. In the second Tl site, Tl(2) is bonded in a single-bond geometry to one O(9) atom. In the third Tl site, Tl(3) is bonded to one O(2), one O(4), one O(5), one O(8), and two equivalent O(9) atoms to form TlO6 octahedra that share corners with two equivalent Tl(3)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, and corners with two equivalent S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form SO4 tetrahedra that share corners with two equivalent Tl(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-42°. In the second S site, S(2) is bonded to one O(2), one O(3), one O(6), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Tl(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. There are nine inequivalent O sites. In the first O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Tl(1) and one S(1) atom. In the second O site, O(8) is bonded in a distorted single-bond geometry to one Tl(1), one Tl(3), and one S(2) atom. In the third O site, O(9) is bonded in a distorted trigonal planar geometry to one Tl(2) and two equivalent Tl(3) atoms. In the fourth O site, O(1) is bonded in a distorted single-bond geometry to one Tl(1) and one S(1) atom. In the fifth O site, O(2) is bonded in a distorted single-bond geometry to one Tl(1), one Tl(3), and one S(2) atom. In the sixth O site, O(3) is bonded in a single-bond geometry to one Tl(1) and one S(2) atom. In the seventh O site, O(4) is bonded in a 2-coordinate geometry to one Tl(1), one Tl(3), and one S(1) atom. In the eighth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Tl(3) and one S(1) atom. In the ninth O site, O(6) is bonded in a single-bond geometry to one S(2) atom.
Tl3S2O9 crystallizes in the monoclinic Cc space group. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom. The Tl(1)-O(1) bond length is 2.55 Å. The Tl(1)-O(2) bond length is 2.73 Å. The Tl(1)-O(3) bond length is 2.79 Å. The Tl(1)-O(4) bond length is 2.88 Å. The Tl(1)-O(7) bond length is 2.62 Å. The Tl(1)-O(8) bond length is 2.82 Å. In the second Tl site, Tl(2) is bonded in a single-bond geometry to one O(9) atom. The Tl(2)-O(9) bond length is 2.70 Å. In the third Tl site, Tl(3) is bonded to one O(2), one O(4), one O(5), one O(8), and two equivalent O(9) atoms to form TlO6 octahedra that share corners with two equivalent Tl(3)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, and corners with two equivalent S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. The Tl(3)-O(2) bond length is 2.51 Å. The Tl(3)-O(4) bond length is 2.50 Å. The Tl(3)-O(5) bond length is 2.56 Å. The Tl(3)-O(8) bond length is 2.53 Å. Both Tl(3)-O(9) bond lengths are 2.05 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form SO4 tetrahedra that share corners with two equivalent Tl(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-42°. The S(1)-O(1) bond length is 1.50 Å. The S(1)-O(4) bond length is 1.50 Å. The S(1)-O(5) bond length is 1.48 Å. The S(1)-O(7) bond length is 1.51 Å. In the second S site, S(2) is bonded to one O(2), one O(3), one O(6), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Tl(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. The S(2)-O(2) bond length is 1.52 Å. The S(2)-O(3) bond length is 1.48 Å. The S(2)-O(6) bond length is 1.47 Å. The S(2)-O(8) bond length is 1.52 Å. There are nine inequivalent O sites. In the first O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Tl(1) and one S(1) atom. In the second O site, O(8) is bonded in a distorted single-bond geometry to one Tl(1), one Tl(3), and one S(2) atom. In the third O site, O(9) is bonded in a distorted trigonal planar geometry to one Tl(2) and two equivalent Tl(3) atoms. In the fourth O site, O(1) is bonded in a distorted single-bond geometry to one Tl(1) and one S(1) atom. In the fifth O site, O(2) is bonded in a distorted single-bond geometry to one Tl(1), one Tl(3), and one S(2) atom. In the sixth O site, O(3) is bonded in a single-bond geometry to one Tl(1) and one S(2) atom. In the seventh O site, O(4) is bonded in a 2-coordinate geometry to one Tl(1), one Tl(3), and one S(1) atom. In the eighth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Tl(3) and one S(1) atom. In the ninth O site, O(6) is bonded in a single-bond geometry to one S(2) atom.