Cs5Re6S8Cl7 crystallizes in the trigonal R3c space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to three equivalent S(1), three equivalent S(2), one Cl(3), and three equivalent Cl(2) atoms. In the third Cs site, Cs(3) is bonded in a 9-coordinate geometry to three equivalent S(1), three equivalent S(2), and three equivalent Cl(1) atoms. There are two inequivalent Re sites. In the first Re site, Re(2) is bonded to one S(1), one S(4), two equivalent S(2), and one Cl(2) atom to form distorted edge-sharing ReS4Cl square pyramids. In the second Re site, Re(1) is bonded to one S(2), one S(3), two equivalent S(1), and one Cl(1) atom to form distorted edge-sharing ReS4Cl square pyramids. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Re(2), and two equivalent Re(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Re(1), and two equivalent Re(2) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to three equivalent Cs(1) and three equivalent Re(1) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to three equivalent Cs(1) and three equivalent Re(2) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Cs(3), two equivalent Cs(1), and one Re(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one Re(2) atom. In the third Cl site, Cl(3) is bonded in a tetrahedral geometry to one Cs(2) and three equivalent Cs(1) atoms.
Cs5Re6S8Cl7 crystallizes in the trigonal R3c space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. The Cs(1)-S(1) bond length is 3.66 Å. The Cs(1)-S(2) bond length is 3.69 Å. The Cs(1)-S(3) bond length is 3.83 Å. The Cs(1)-S(4) bond length is 3.84 Å. The Cs(1)-Cl(3) bond length is 3.31 Å. There is one shorter (3.82 Å) and one longer (3.87 Å) Cs(1)-Cl(1) bond length. There is one shorter (3.82 Å) and one longer (3.91 Å) Cs(1)-Cl(2) bond length. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to three equivalent S(1), three equivalent S(2), one Cl(3), and three equivalent Cl(2) atoms. All Cs(2)-S(1) bond lengths are 3.63 Å. All Cs(2)-S(2) bond lengths are 4.01 Å. The Cs(2)-Cl(3) bond length is 3.67 Å. All Cs(2)-Cl(2) bond lengths are 3.73 Å. In the third Cs site, Cs(3) is bonded in a 9-coordinate geometry to three equivalent S(1), three equivalent S(2), and three equivalent Cl(1) atoms. All Cs(3)-S(1) bond lengths are 4.00 Å. All Cs(3)-S(2) bond lengths are 3.66 Å. All Cs(3)-Cl(1) bond lengths are 3.66 Å. There are two inequivalent Re sites. In the first Re site, Re(2) is bonded to one S(1), one S(4), two equivalent S(2), and one Cl(2) atom to form distorted edge-sharing ReS4Cl square pyramids. The Re(2)-S(1) bond length is 2.42 Å. The Re(2)-S(4) bond length is 2.43 Å. Both Re(2)-S(2) bond lengths are 2.43 Å. The Re(2)-Cl(2) bond length is 2.45 Å. In the second Re site, Re(1) is bonded to one S(2), one S(3), two equivalent S(1), and one Cl(1) atom to form distorted edge-sharing ReS4Cl square pyramids. The Re(1)-S(2) bond length is 2.43 Å. The Re(1)-S(3) bond length is 2.43 Å. There is one shorter (2.42 Å) and one longer (2.43 Å) Re(1)-S(1) bond length. The Re(1)-Cl(1) bond length is 2.44 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Re(2), and two equivalent Re(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), one Re(1), and two equivalent Re(2) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to three equivalent Cs(1) and three equivalent Re(1) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to three equivalent Cs(1) and three equivalent Re(2) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Cs(3), two equivalent Cs(1), and one Re(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one Re(2) atom. In the third Cl site, Cl(3) is bonded in a tetrahedral geometry to one Cs(2) and three equivalent Cs(1) atoms.