Rb3Bi2S2(O2Cl)5 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one O(2), one O(6), one O(7), one O(8), one O(9), one Cl(3), one Cl(4), and one Cl(5) atom. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(8), one O(9), one Cl(1), one Cl(2), and one Cl(3) atom. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(3), one O(6), one Cl(1), one Cl(2), one Cl(4), and one Cl(5) atom. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), one Cl(1), one Cl(2), and one Cl(3) atom. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(4), one O(5), one O(6), one O(7), one O(8), one Cl(3), one Cl(4), and one Cl(5) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second S site, S(2) is bonded in a tetrahedral geometry to one O(5), one O(6), one O(7), and one O(8) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), one Bi(1), and one S(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), one Bi(1), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), one Bi(1), and one S(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Bi(1), one Bi(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one Bi(1), one Bi(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(3), one Bi(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Rb(1), one Bi(2), and one S(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), one Bi(2), and one S(2) atom. In the ninth O site, O(9) is bonded in a T-shaped geometry to one Rb(1), one Rb(2), and one O(10) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Rb(3) and one O(9) atom. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), and one Bi(1) atom. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Rb(2), one Rb(3), and one Bi(1) atom. In the third Cl site, Cl(3) is bonded in a square co-planar geometry to one Rb(1), one Rb(2), one Bi(1), and one Bi(2) atom. In the fourth Cl site, Cl(4) is bonded in a distorted T-shaped geometry to one Rb(1), one Rb(3), and one Bi(2) atom. In the fifth Cl site, Cl(5) is bonded in a distorted T-shaped geometry to one Rb(1), one Rb(3), and one Bi(2) atom.
Rb3Bi2S2(O2Cl)5 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one O(2), one O(6), one O(7), one O(8), one O(9), one Cl(3), one Cl(4), and one Cl(5) atom. The Rb(1)-O(2) bond length is 2.85 Å. The Rb(1)-O(6) bond length is 3.06 Å. The Rb(1)-O(7) bond length is 2.96 Å. The Rb(1)-O(8) bond length is 3.07 Å. The Rb(1)-O(9) bond length is 3.49 Å. The Rb(1)-Cl(3) bond length is 3.53 Å. The Rb(1)-Cl(4) bond length is 3.61 Å. The Rb(1)-Cl(5) bond length is 3.64 Å. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(8), one O(9), one Cl(1), one Cl(2), and one Cl(3) atom. The Rb(2)-O(1) bond length is 2.97 Å. The Rb(2)-O(2) bond length is 3.11 Å. The Rb(2)-O(3) bond length is 3.02 Å. The Rb(2)-O(8) bond length is 2.82 Å. The Rb(2)-O(9) bond length is 3.37 Å. The Rb(2)-Cl(1) bond length is 3.59 Å. The Rb(2)-Cl(2) bond length is 3.74 Å. The Rb(2)-Cl(3) bond length is 3.49 Å. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(3), one O(6), one Cl(1), one Cl(2), one Cl(4), and one Cl(5) atom. The Rb(3)-O(1) bond length is 3.47 Å. The Rb(3)-O(10) bond length is 3.25 Å. The Rb(3)-O(3) bond length is 3.06 Å. The Rb(3)-O(6) bond length is 3.19 Å. The Rb(3)-Cl(1) bond length is 3.80 Å. The Rb(3)-Cl(2) bond length is 3.44 Å. The Rb(3)-Cl(4) bond length is 3.42 Å. The Rb(3)-Cl(5) bond length is 3.53 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), one Cl(1), one Cl(2), and one Cl(3) atom. The Bi(1)-O(1) bond length is 2.56 Å. The Bi(1)-O(2) bond length is 2.65 Å. The Bi(1)-O(3) bond length is 2.44 Å. The Bi(1)-O(4) bond length is 2.72 Å. The Bi(1)-O(5) bond length is 2.82 Å. The Bi(1)-Cl(1) bond length is 2.57 Å. The Bi(1)-Cl(2) bond length is 2.63 Å. The Bi(1)-Cl(3) bond length is 2.97 Å. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(4), one O(5), one O(6), one O(7), one O(8), one Cl(3), one Cl(4), and one Cl(5) atom. The Bi(2)-O(4) bond length is 2.79 Å. The Bi(2)-O(5) bond length is 2.70 Å. The Bi(2)-O(6) bond length is 2.45 Å. The Bi(2)-O(7) bond length is 2.51 Å. The Bi(2)-O(8) bond length is 2.70 Å. The Bi(2)-Cl(3) bond length is 3.09 Å. The Bi(2)-Cl(4) bond length is 2.57 Å. The Bi(2)-Cl(5) bond length is 2.60 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The S(1)-O(1) bond length is 1.50 Å. The S(1)-O(2) bond length is 1.49 Å. The S(1)-O(3) bond length is 1.52 Å. The S(1)-O(4) bond length is 1.49 Å. In the second S site, S(2) is bonded in a tetrahedral geometry to one O(5), one O(6), one O(7), and one O(8) atom. The S(2)-O(5) bond length is 1.49 Å. The S(2)-O(6) bond length is 1.52 Å. The S(2)-O(7) bond length is 1.50 Å. The S(2)-O(8) bond length is 1.49 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), one Bi(1), and one S(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), one Bi(1), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), one Bi(1), and one S(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Bi(1), one Bi(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one Bi(1), one Bi(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(3), one Bi(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Rb(1), one Bi(2), and one S(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), one Bi(2), and one S(2) atom. In the ninth O site, O(9) is bonded in a T-shaped geometry to one Rb(1), one Rb(2), and one O(10) atom. The O(9)-O(10) bond length is 1.24 Å. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Rb(3) and one O(9) atom. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), and one Bi(1) atom. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Rb(2), one Rb(3), and one Bi(1) atom. In the third Cl site, Cl(3) is bonded in a square co-planar geometry to one Rb(1), one Rb(2), one Bi(1), and one Bi(2) atom. In the fourth Cl site, Cl(4) is bonded in a distorted T-shaped geometry to one Rb(1), one Rb(3), and one Bi(2) atom. In the fifth Cl site, Cl(5) is bonded in a distorted T-shaped geometry to one Rb(1), one Rb(3), and one Bi(2) atom.