Rb4Tc6S13 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 8-coordinate geometry to one S(1), one S(2), one S(3), one S(6), two equivalent S(5), and two equivalent S(7) atoms. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(4), one S(6), one S(7), and two equivalent S(3) atoms. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one S(3), one S(4), one S(5), one S(6), and one S(7) atom to form edge-sharing TcS5 square pyramids. In the second Tc site, Tc(2) is bonded to one S(1), one S(4), one S(5), one S(6), and one S(7) atom to form a mixture of distorted corner and edge-sharing TcS5 square pyramids. In the third Tc site, Tc(3) is bonded to one S(2), one S(4), one S(5), one S(6), and one S(7) atom to form TcS5 square pyramids that share  a cornercorner with one S(2)Rb2TcS tetrahedra, edges with two equivalent Tc(1)S5 square pyramids, and edges with two equivalent Tc(2)S5 square pyramids. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Tc(2) atoms. In the second S site, S(2) is bonded to one Rb(1), one Rb(2), one Tc(3), and one S(2) atom to form distorted SRb2TcS tetrahedra that share  a cornercorner with one Tc(3)S5 square pyramid. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Tc(1), and one S(3) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Rb(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Rb(2), two equivalent Rb(1), one Tc(1), one Tc(2), and one Tc(3) atom.
Rb4Tc6S13 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 8-coordinate geometry to one S(1), one S(2), one S(3), one S(6), two equivalent S(5), and two equivalent S(7) atoms. The Rb(1)-S(1) bond length is 3.40 Å. The Rb(1)-S(2) bond length is 3.40 Å. The Rb(1)-S(3) bond length is 3.35 Å. The Rb(1)-S(6) bond length is 3.71 Å. There is one shorter (3.20 Å) and one longer (3.45 Å) Rb(1)-S(5) bond length. There is one shorter (3.25 Å) and one longer (3.80 Å) Rb(1)-S(7) bond length. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(4), one S(6), one S(7), and two equivalent S(3) atoms. The Rb(2)-S(1) bond length is 3.85 Å. The Rb(2)-S(2) bond length is 3.22 Å. The Rb(2)-S(4) bond length is 3.36 Å. The Rb(2)-S(6) bond length is 3.42 Å. The Rb(2)-S(7) bond length is 3.24 Å. There is one shorter (3.36 Å) and one longer (3.37 Å) Rb(2)-S(3) bond length. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one S(3), one S(4), one S(5), one S(6), and one S(7) atom to form edge-sharing TcS5 square pyramids. The Tc(1)-S(3) bond length is 2.52 Å. The Tc(1)-S(4) bond length is 2.38 Å. The Tc(1)-S(5) bond length is 2.39 Å. The Tc(1)-S(6) bond length is 2.41 Å. The Tc(1)-S(7) bond length is 2.38 Å. In the second Tc site, Tc(2) is bonded to one S(1), one S(4), one S(5), one S(6), and one S(7) atom to form a mixture of distorted corner and edge-sharing TcS5 square pyramids. The Tc(2)-S(1) bond length is 2.48 Å. The Tc(2)-S(4) bond length is 2.38 Å. The Tc(2)-S(5) bond length is 2.42 Å. The Tc(2)-S(6) bond length is 2.40 Å. The Tc(2)-S(7) bond length is 2.41 Å. In the third Tc site, Tc(3) is bonded to one S(2), one S(4), one S(5), one S(6), and one S(7) atom to form TcS5 square pyramids that share  a cornercorner with one S(2)Rb2TcS tetrahedra, edges with two equivalent Tc(1)S5 square pyramids, and edges with two equivalent Tc(2)S5 square pyramids. The Tc(3)-S(2) bond length is 2.44 Å. The Tc(3)-S(4) bond length is 2.39 Å. The Tc(3)-S(5) bond length is 2.42 Å. The Tc(3)-S(6) bond length is 2.39 Å. The Tc(3)-S(7) bond length is 2.37 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Tc(2) atoms. In the second S site, S(2) is bonded to one Rb(1), one Rb(2), one Tc(3), and one S(2) atom to form distorted SRb2TcS tetrahedra that share  a cornercorner with one Tc(3)S5 square pyramid. The S(2)-S(2) bond length is 2.08 Å. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Tc(1), and one S(3) atom. The S(3)-S(3) bond length is 2.10 Å. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Rb(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Rb(2), two equivalent Rb(1), one Tc(1), one Tc(2), and one Tc(3) atom.