Cs4Tc6S13 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to one Cs(2), one S(3), two equivalent S(1), two equivalent S(4), two equivalent S(5), two equivalent S(6), and two equivalent S(7) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Cs(1), one S(1), one S(2), one S(3), one S(4), one S(6), and one S(7) atom. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one S(1), one S(2), one S(4), one S(5), 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(2), one S(3), one S(4), and one S(5) atom to form a mixture of corner and edge-sharing TcS5 square pyramids. In the third Tc site, Tc(3) is bonded to one S(1), one S(2), one S(4), one S(5), and one S(6) atom to form distorted edge-sharing TcS5 square pyramids. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Cs(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Tc(2) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the fifth S site, S(5) is bonded to two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom to form distorted edge-sharing SCs2Tc3 square pyramids. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(3), and one S(6) atom. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(1), and one S(7) atom.
Cs4Tc6S13 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to one Cs(2), one S(3), two equivalent S(1), two equivalent S(4), two equivalent S(5), two equivalent S(6), and two equivalent S(7) atoms. The Cs(1)-Cs(2) bond length is 3.87 Å. The Cs(1)-S(3) bond length is 3.97 Å. There is one shorter (4.15 Å) and one longer (4.18 Å) Cs(1)-S(1) bond length. There is one shorter (3.60 Å) and one longer (3.70 Å) Cs(1)-S(4) bond length. There is one shorter (3.37 Å) and one longer (3.40 Å) Cs(1)-S(5) bond length. There is one shorter (3.90 Å) and one longer (4.07 Å) Cs(1)-S(6) bond length. There is one shorter (3.51 Å) and one longer (3.64 Å) Cs(1)-S(7) bond length. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Cs(1), one S(1), one S(2), one S(3), one S(4), one S(6), and one S(7) atom. The Cs(2)-S(1) bond length is 3.68 Å. The Cs(2)-S(2) bond length is 3.34 Å. The Cs(2)-S(3) bond length is 3.44 Å. The Cs(2)-S(4) bond length is 3.45 Å. The Cs(2)-S(6) bond length is 3.35 Å. The Cs(2)-S(7) bond length is 3.43 Å. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one S(1), one S(2), one S(4), one S(5), and one S(7) atom to form edge-sharing TcS5 square pyramids. The Tc(1)-S(1) bond length is 2.41 Å. The Tc(1)-S(2) bond length is 2.39 Å. The Tc(1)-S(4) bond length is 2.38 Å. The Tc(1)-S(5) bond length is 2.38 Å. The Tc(1)-S(7) bond length is 2.58 Å. In the second Tc site, Tc(2) is bonded to one S(1), one S(2), one S(3), one S(4), and one S(5) atom to form a mixture of corner and edge-sharing TcS5 square pyramids. The Tc(2)-S(1) bond length is 2.42 Å. The Tc(2)-S(2) bond length is 2.36 Å. The Tc(2)-S(3) bond length is 2.46 Å. The Tc(2)-S(4) bond length is 2.41 Å. The Tc(2)-S(5) bond length is 2.37 Å. In the third Tc site, Tc(3) is bonded to one S(1), one S(2), one S(4), one S(5), and one S(6) atom to form distorted edge-sharing TcS5 square pyramids. The Tc(3)-S(1) bond length is 2.41 Å. The Tc(3)-S(2) bond length is 2.40 Å. The Tc(3)-S(4) bond length is 2.38 Å. The Tc(3)-S(5) bond length is 2.40 Å. The Tc(3)-S(6) bond length is 2.45 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Cs(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Tc(2) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the fifth S site, S(5) is bonded to two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom to form distorted edge-sharing SCs2Tc3 square pyramids. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(3), and one S(6) atom. The S(6)-S(6) bond length is 2.08 Å. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Tc(1), and one S(7) atom. The S(7)-S(7) bond length is 2.12 Å.