Cs4(BS)9 crystallizes in the triclinic P-1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to one B(8), one B(9), one S(3), one S(6), one S(8), one S(9), two equivalent S(2), and two equivalent S(7) atoms. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(4), one S(5), one S(9), and two equivalent S(8) atoms. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one S(4), one S(6), one S(8), two equivalent S(7), and two equivalent S(9) atoms. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to one S(1), one S(2), one S(4), one S(7), one S(8), one S(9), and two equivalent S(5) atoms. There are nine inequivalent B sites. In the first B site, B(1) is bonded in a distorted single-bond geometry to one S(1) atom. In the second B site, B(2) is bonded in a distorted single-bond geometry to one S(2) atom. In the third B site, B(3) is bonded in a distorted single-bond geometry to one S(3) atom. In the fourth B site, B(4) is bonded in a distorted single-bond geometry to one S(4) atom. In the fifth B site, B(5) is bonded in a distorted single-bond geometry to one S(5) atom. In the sixth B site, B(6) is bonded in a distorted single-bond geometry to one S(6) atom. In the seventh B site, B(7) is bonded in a trigonal planar geometry to one S(1), one S(2), and one S(7) atom. In the eighth B site, B(8) is bonded in a trigonal planar geometry to one Cs(1), one S(3), one S(4), and one S(8) atom. In the ninth B site, B(9) is bonded in a trigonal planar geometry to one Cs(1), one S(5), one S(6), and one S(9) atom. There are nine inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one Cs(2), one Cs(4), one B(1), and one B(7) atom. In the second S site, S(2) is bonded in a distorted water-like geometry to one Cs(4), two equivalent Cs(1), one B(2), and one B(7) atom. In the third S site, S(3) is bonded in a distorted water-like geometry to one Cs(1), one Cs(2), one B(3), and one B(8) atom. In the fourth S site, S(4) is bonded in a distorted water-like geometry to one Cs(2), one Cs(3), one Cs(4), one B(4), and one B(8) atom. In the fifth S site, S(5) is bonded in a distorted water-like geometry to one Cs(2), two equivalent Cs(4), one B(5), and one B(9) atom. In the sixth S site, S(6) is bonded in a distorted water-like geometry to one Cs(1), one Cs(3), one B(6), and one B(9) atom. In the seventh S site, S(7) is bonded in a distorted single-bond geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and one B(7) atom. In the eighth S site, S(8) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), one Cs(4), two equivalent Cs(2), and one B(8) atom. In the ninth S site, S(9) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one B(9) atom.
Cs4(BS)9 crystallizes in the triclinic P-1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to one B(8), one B(9), one S(3), one S(6), one S(8), one S(9), two equivalent S(2), and two equivalent S(7) atoms. The Cs(1)-B(8) bond length is 3.66 Å. The Cs(1)-B(9) bond length is 3.78 Å. The Cs(1)-S(3) bond length is 3.68 Å. The Cs(1)-S(6) bond length is 3.54 Å. The Cs(1)-S(8) bond length is 3.66 Å. The Cs(1)-S(9) bond length is 3.85 Å. Both Cs(1)-S(2) bond lengths are 3.81 Å. There is one shorter (3.53 Å) and one longer (3.68 Å) Cs(1)-S(7) bond length. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(4), one S(5), one S(9), and two equivalent S(8) atoms. The Cs(2)-S(1) bond length is 3.58 Å. The Cs(2)-S(3) bond length is 3.53 Å. The Cs(2)-S(4) bond length is 3.65 Å. The Cs(2)-S(5) bond length is 3.65 Å. The Cs(2)-S(9) bond length is 3.49 Å. There is one shorter (3.55 Å) and one longer (3.60 Å) Cs(2)-S(8) bond length. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one S(4), one S(6), one S(8), two equivalent S(7), and two equivalent S(9) atoms. The Cs(3)-S(4) bond length is 3.78 Å. The Cs(3)-S(6) bond length is 3.62 Å. The Cs(3)-S(8) bond length is 3.47 Å. There is one shorter (3.65 Å) and one longer (3.77 Å) Cs(3)-S(7) bond length. There is one shorter (3.55 Å) and one longer (3.80 Å) Cs(3)-S(9) bond length. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to one S(1), one S(2), one S(4), one S(7), one S(8), one S(9), and two equivalent S(5) atoms. The Cs(4)-S(1) bond length is 4.00 Å. The Cs(4)-S(2) bond length is 3.65 Å. The Cs(4)-S(4) bond length is 4.05 Å. The Cs(4)-S(7) bond length is 4.08 Å. The Cs(4)-S(8) bond length is 3.67 Å. The Cs(4)-S(9) bond length is 3.72 Å. There is one shorter (3.71 Å) and one longer (3.72 Å) Cs(4)-S(5) bond length. There are nine inequivalent B sites. In the first B site, B(1) is bonded in a distorted single-bond geometry to one S(1) atom. The B(1)-S(1) bond length is 1.86 Å. In the second B site, B(2) is bonded in a distorted single-bond geometry to one S(2) atom. The B(2)-S(2) bond length is 1.87 Å. In the third B site, B(3) is bonded in a distorted single-bond geometry to one S(3) atom. The B(3)-S(3) bond length is 1.85 Å. In the fourth B site, B(4) is bonded in a distorted single-bond geometry to one S(4) atom. The B(4)-S(4) bond length is 1.86 Å. In the fifth B site, B(5) is bonded in a distorted single-bond geometry to one S(5) atom. The B(5)-S(5) bond length is 1.86 Å. In the sixth B site, B(6) is bonded in a distorted single-bond geometry to one S(6) atom. The B(6)-S(6) bond length is 1.85 Å. In the seventh B site, B(7) is bonded in a trigonal planar geometry to one S(1), one S(2), and one S(7) atom. The B(7)-S(1) bond length is 1.85 Å. The B(7)-S(2) bond length is 1.86 Å. The B(7)-S(7) bond length is 1.77 Å. In the eighth B site, B(8) is bonded in a trigonal planar geometry to one Cs(1), one S(3), one S(4), and one S(8) atom. The B(8)-S(3) bond length is 1.84 Å. The B(8)-S(4) bond length is 1.86 Å. The B(8)-S(8) bond length is 1.77 Å. In the ninth B site, B(9) is bonded in a trigonal planar geometry to one Cs(1), one S(5), one S(6), and one S(9) atom. The B(9)-S(5) bond length is 1.86 Å. The B(9)-S(6) bond length is 1.84 Å. The B(9)-S(9) bond length is 1.76 Å. There are nine inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one Cs(2), one Cs(4), one B(1), and one B(7) atom. In the second S site, S(2) is bonded in a distorted water-like geometry to one Cs(4), two equivalent Cs(1), one B(2), and one B(7) atom. In the third S site, S(3) is bonded in a distorted water-like geometry to one Cs(1), one Cs(2), one B(3), and one B(8) atom. In the fourth S site, S(4) is bonded in a distorted water-like geometry to one Cs(2), one Cs(3), one Cs(4), one B(4), and one B(8) atom. In the fifth S site, S(5) is bonded in a distorted water-like geometry to one Cs(2), two equivalent Cs(4), one B(5), and one B(9) atom. In the sixth S site, S(6) is bonded in a distorted water-like geometry to one Cs(1), one Cs(3), one B(6), and one B(9) atom. In the seventh S site, S(7) is bonded in a distorted single-bond geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and one B(7) atom. In the eighth S site, S(8) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), one Cs(4), two equivalent Cs(2), and one B(8) atom. In the ninth S site, S(9) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one B(9) atom.