Cs5Tc6S8Br7 crystallizes in the trigonal R-3c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), one Br(2), and four equivalent Br(1) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to three equivalent S(1) and three equivalent Br(1) atoms. Tc(1) is bonded to one S(2), three equivalent S(1), and one Br(1) atom to form edge-sharing TcS4Br square pyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), and three equivalent Tc(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to three equivalent Cs(1) and three equivalent Tc(1) atoms. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one Tc(1) atom. In the second Br site, Br(2) is bonded in a trigonal planar geometry to three equivalent Cs(1) atoms.
Cs5Tc6S8Br7 crystallizes in the trigonal R-3c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), one Br(2), and four equivalent Br(1) atoms. Both Cs(1)-S(1) bond lengths are 3.82 Å. Both Cs(1)-S(2) bond lengths are 3.88 Å. The Cs(1)-Br(2) bond length is 3.42 Å. There are two shorter (3.91 Å) and two longer (3.93 Å) Cs(1)-Br(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to three equivalent S(1) and three equivalent Br(1) atoms. All Cs(2)-S(1) bond lengths are 3.70 Å. All Cs(2)-Br(1) bond lengths are 4.03 Å. Tc(1) is bonded to one S(2), three equivalent S(1), and one Br(1) atom to form edge-sharing TcS4Br square pyramids. The Tc(1)-S(2) bond length is 2.41 Å. There is one shorter (2.39 Å) and two longer (2.40 Å) Tc(1)-S(1) bond lengths. The Tc(1)-Br(1) bond length is 2.60 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), and three equivalent Tc(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to three equivalent Cs(1) and three equivalent Tc(1) atoms. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one Tc(1) atom. In the second Br site, Br(2) is bonded in a trigonal planar geometry to three equivalent Cs(1) atoms.