KBi(PS3)2 crystallizes in the monoclinic P2_1 space group. K(1) is bonded in a 9-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms. Bi(1) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(5), two equivalent S(4), and two equivalent S(6) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded in a distorted tetrahedral geometry to one P(2), one S(1), one S(4), and one S(6) atom. In the second P site, P(2) is bonded in a distorted tetrahedral geometry to one P(1), one S(2), one S(3), and one S(5) atom. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted single-bond geometry to two equivalent K(1), one Bi(1), and one P(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to three equivalent K(1) and one P(2) atom. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Bi(1), and one P(2) atom. In the fourth S site, S(4) is bonded in a distorted water-like geometry to two equivalent Bi(1) and one P(1) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one K(1), one Bi(1), and one P(2) atom. In the sixth S site, S(6) is bonded in a 1-coordinate geometry to one K(1), two equivalent Bi(1), and one P(1) atom.
KBi(PS3)2 crystallizes in the monoclinic P2_1 space group. K(1) is bonded in a 9-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms. The K(1)-S(5) bond length is 3.69 Å. The K(1)-S(6) bond length is 3.62 Å. There is one shorter (3.47 Å) and one longer (3.52 Å) K(1)-S(1) bond length. There is one shorter (3.31 Å) and one longer (3.38 Å) K(1)-S(3) bond length. There are a spread of K(1)-S(2) bond distances ranging from 3.26-3.58 Å. Bi(1) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(5), two equivalent S(4), and two equivalent S(6) atoms. The Bi(1)-S(1) bond length is 3.13 Å. The Bi(1)-S(3) bond length is 2.84 Å. The Bi(1)-S(5) bond length is 2.76 Å. There is one shorter (2.77 Å) and one longer (3.24 Å) Bi(1)-S(4) bond length. There is one shorter (2.93 Å) and one longer (3.22 Å) Bi(1)-S(6) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded in a distorted tetrahedral geometry to one P(2), one S(1), one S(4), and one S(6) atom. The P(1)-P(2) bond length is 2.26 Å. The P(1)-S(1) bond length is 2.01 Å. The P(1)-S(4) bond length is 2.08 Å. The P(1)-S(6) bond length is 2.06 Å. In the second P site, P(2) is bonded in a distorted tetrahedral geometry to one P(1), one S(2), one S(3), and one S(5) atom. The P(2)-S(2) bond length is 1.98 Å. The P(2)-S(3) bond length is 2.04 Å. The P(2)-S(5) bond length is 2.07 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted single-bond geometry to two equivalent K(1), one Bi(1), and one P(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to three equivalent K(1) and one P(2) atom. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Bi(1), and one P(2) atom. In the fourth S site, S(4) is bonded in a distorted water-like geometry to two equivalent Bi(1) and one P(1) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one K(1), one Bi(1), and one P(2) atom. In the sixth S site, S(6) is bonded in a 1-coordinate geometry to one K(1), two equivalent Bi(1), and one P(1) atom.