K3Sn2S3O12Br crystallizes in the monoclinic P2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(4), one O(5), one O(6), one O(8), and one O(9) atom. In the third K site, K(3) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(4), one O(7), one O(8), one O(9), and two equivalent Br(1) atoms. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 3-coordinate geometry to one O(1), one O(6), one O(9), and one Br(1) atom. In the second Sn site, Sn(2) is bonded in a 3-coordinate geometry to one O(3), one O(7), one O(8), and two equivalent Br(1) atoms. There are three 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(11), one O(5), one O(6), and one O(9) atom. In the third S site, S(3) is bonded in a tetrahedral geometry to one O(10), one O(12), one O(7), and one O(8) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one K(1), one Sn(1), and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one K(2) and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(1), one K(2), one Sn(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one K(1), one K(2), one K(3), and one S(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one K(1), one K(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one K(1), one K(2), one Sn(1), and one S(2) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one K(1), one K(3), one Sn(2), and one S(3) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one K(2), one K(3), one Sn(2), and one S(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one K(2), one K(3), one Sn(1), and one S(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one K(1), one K(2), one K(3), and one S(3) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one K(1), one K(3), and one S(2) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one S(3) atom. Br(1) is bonded to two equivalent K(3), one Sn(1), and two equivalent Sn(2) atoms to form distorted edge-sharing BrK2Sn3 square pyramids.
K3Sn2S3O12Br crystallizes in the monoclinic P2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The K(1)-O(1) bond length is 3.08 Å. The K(1)-O(10) bond length is 2.80 Å. The K(1)-O(11) bond length is 2.95 Å. The K(1)-O(12) bond length is 2.81 Å. The K(1)-O(3) bond length is 2.97 Å. The K(1)-O(4) bond length is 2.96 Å. The K(1)-O(5) bond length is 2.68 Å. The K(1)-O(6) bond length is 2.85 Å. The K(1)-O(7) bond length is 3.06 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(4), one O(5), one O(6), one O(8), and one O(9) atom. The K(2)-O(10) bond length is 2.80 Å. The K(2)-O(12) bond length is 2.85 Å. The K(2)-O(2) bond length is 2.96 Å. The K(2)-O(3) bond length is 2.87 Å. The K(2)-O(4) bond length is 2.80 Å. The K(2)-O(5) bond length is 2.70 Å. The K(2)-O(6) bond length is 2.82 Å. The K(2)-O(8) bond length is 3.12 Å. The K(2)-O(9) bond length is 2.99 Å. In the third K site, K(3) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(4), one O(7), one O(8), one O(9), and two equivalent Br(1) atoms. The K(3)-O(10) bond length is 2.66 Å. The K(3)-O(11) bond length is 2.87 Å. The K(3)-O(4) bond length is 3.01 Å. The K(3)-O(7) bond length is 2.78 Å. The K(3)-O(8) bond length is 2.80 Å. The K(3)-O(9) bond length is 3.22 Å. There is one shorter (3.21 Å) and one longer (3.36 Å) K(3)-Br(1) bond length. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 3-coordinate geometry to one O(1), one O(6), one O(9), and one Br(1) atom. The Sn(1)-O(1) bond length is 2.34 Å. The Sn(1)-O(6) bond length is 2.29 Å. The Sn(1)-O(9) bond length is 2.42 Å. The Sn(1)-Br(1) bond length is 3.19 Å. In the second Sn site, Sn(2) is bonded in a 3-coordinate geometry to one O(3), one O(7), one O(8), and two equivalent Br(1) atoms. The Sn(2)-O(3) bond length is 2.55 Å. The Sn(2)-O(7) bond length is 2.34 Å. The Sn(2)-O(8) bond length is 2.38 Å. There is one shorter (3.12 Å) and one longer (3.33 Å) Sn(2)-Br(1) bond length. There are three 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 1.54 Å. The S(1)-O(2) bond length is 1.50 Å. The S(1)-O(3) bond length is 1.50 Å. The S(1)-O(4) bond length is 1.47 Å. In the second S site, S(2) is bonded in a tetrahedral geometry to one O(11), one O(5), one O(6), and one O(9) atom. The S(2)-O(11) bond length is 1.47 Å. The S(2)-O(5) bond length is 1.47 Å. The S(2)-O(6) bond length is 1.53 Å. The S(2)-O(9) bond length is 1.52 Å. In the third S site, S(3) is bonded in a tetrahedral geometry to one O(10), one O(12), one O(7), and one O(8) atom. The S(3)-O(10) bond length is 1.47 Å. The S(3)-O(12) bond length is 1.47 Å. The S(3)-O(7) bond length is 1.53 Å. The S(3)-O(8) bond length is 1.52 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one K(1), one Sn(1), and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one K(2) and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(1), one K(2), one Sn(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one K(1), one K(2), one K(3), and one S(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one K(1), one K(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one K(1), one K(2), one Sn(1), and one S(2) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one K(1), one K(3), one Sn(2), and one S(3) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one K(2), one K(3), one Sn(2), and one S(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one K(2), one K(3), one Sn(1), and one S(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one K(1), one K(2), one K(3), and one S(3) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one K(1), one K(3), and one S(2) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one S(3) atom. Br(1) is bonded to two equivalent K(3), one Sn(1), and two equivalent Sn(2) atoms to form distorted edge-sharing BrK2Sn3 square pyramids.