Cs4Re6S13 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 4-coordinate geometry to two equivalent S(3), two equivalent S(5), and two equivalent S(6) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(7) atom. There are three inequivalent Re sites. In the first Re site, Re(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 ReS5 square pyramids. In the second Re site, Re(2) is bonded to one S(2), one S(4), one S(5), one S(6), and one S(7) atom to form a mixture of corner and edge-sharing ReS5 square pyramids. In the third Re site, Re(3) is bonded to one S(1), one S(4), one S(5), one S(6), and one S(7) atom to form distorted edge-sharing ReS5 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), one Re(3), and one S(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Cs(2) and two equivalent Re(2) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), and one S(3) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Cs(2), one Re(1), one Re(2), and one Re(3) atom. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom. In the sixth S site, S(6) is bonded to two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom to form distorted edge-sharing SCs2Re3 square pyramids. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one Cs(2), one Re(1), one Re(2), and one Re(3) atom.
Cs4Re6S13 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 4-coordinate geometry to two equivalent S(3), two equivalent S(5), and two equivalent S(6) atoms. There is one shorter (3.50 Å) and one longer (3.68 Å) Cs(1)-S(3) bond length. There is one shorter (3.58 Å) and one longer (3.71 Å) Cs(1)-S(5) bond length. There is one shorter (3.37 Å) and one longer (3.39 Å) Cs(1)-S(6) bond length. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(7) atom. The Cs(2)-S(1) bond length is 3.34 Å. The Cs(2)-S(2) bond length is 3.45 Å. The Cs(2)-S(3) bond length is 3.44 Å. The Cs(2)-S(4) bond length is 3.67 Å. The Cs(2)-S(5) bond length is 3.44 Å. The Cs(2)-S(7) bond length is 3.33 Å. There are three inequivalent Re sites. In the first Re site, Re(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 ReS5 square pyramids. The Re(1)-S(3) bond length is 2.56 Å. The Re(1)-S(4) bond length is 2.43 Å. The Re(1)-S(5) bond length is 2.41 Å. The Re(1)-S(6) bond length is 2.40 Å. The Re(1)-S(7) bond length is 2.41 Å. In the second Re site, Re(2) is bonded to one S(2), one S(4), one S(5), one S(6), and one S(7) atom to form a mixture of corner and edge-sharing ReS5 square pyramids. The Re(2)-S(2) bond length is 2.46 Å. The Re(2)-S(4) bond length is 2.44 Å. The Re(2)-S(5) bond length is 2.43 Å. The Re(2)-S(6) bond length is 2.40 Å. The Re(2)-S(7) bond length is 2.39 Å. In the third Re site, Re(3) is bonded to one S(1), one S(4), one S(5), one S(6), and one S(7) atom to form distorted edge-sharing ReS5 square pyramids. The Re(3)-S(1) bond length is 2.44 Å. The Re(3)-S(4) bond length is 2.43 Å. The Re(3)-S(5) bond length is 2.41 Å. The Re(3)-S(6) bond length is 2.42 Å. The Re(3)-S(7) bond length is 2.42 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), one Re(3), and one S(1) atom. The S(1)-S(1) bond length is 2.10 Å. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Cs(2) and two equivalent Re(2) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), and one S(3) atom. The S(3)-S(3) bond length is 2.14 Å. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Cs(2), one Re(1), one Re(2), and one Re(3) atom. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom. In the sixth S site, S(6) is bonded to two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom to form distorted edge-sharing SCs2Re3 square pyramids. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one Cs(2), one Re(1), one Re(2), and one Re(3) atom.