KBi(PSe3)2 crystallizes in the monoclinic P2_1 space group. K(1) is bonded in a 9-coordinate geometry to one Se(3), one Se(6), two equivalent Se(4), two equivalent Se(5), and three equivalent Se(2) atoms. Bi(1) is bonded in a 7-coordinate geometry to one Se(4), one Se(5), one Se(6), two equivalent Se(1), and two equivalent Se(3) 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 Se(1), one Se(3), and one Se(5) atom. In the second P site, P(2) is bonded in a distorted tetrahedral geometry to one P(1), one Se(2), one Se(4), and one Se(6) atom. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted water-like geometry to two equivalent Bi(1) and one P(1) atom. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to three equivalent K(1) and one P(2) atom. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to one K(1), two equivalent Bi(1), and one P(1) atom. In the fourth Se site, Se(4) 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 fifth Se site, Se(5) is bonded in a 4-coordinate geometry to two equivalent K(1), one Bi(1), and one P(1) atom. In the sixth Se site, Se(6) is bonded in a distorted T-shaped geometry to one K(1), one Bi(1), and one P(2) atom.
KBi(PSe3)2 crystallizes in the monoclinic P2_1 space group. K(1) is bonded in a 9-coordinate geometry to one Se(3), one Se(6), two equivalent Se(4), two equivalent Se(5), and three equivalent Se(2) atoms. The K(1)-Se(3) bond length is 3.71 Å. The K(1)-Se(6) bond length is 3.71 Å. There is one shorter (3.37 Å) and one longer (3.44 Å) K(1)-Se(4) bond length. There is one shorter (3.49 Å) and one longer (3.51 Å) K(1)-Se(5) bond length. There are a spread of K(1)-Se(2) bond distances ranging from 3.37-3.75 Å. Bi(1) is bonded in a 7-coordinate geometry to one Se(4), one Se(5), one Se(6), two equivalent Se(1), and two equivalent Se(3) atoms. The Bi(1)-Se(4) bond length is 3.00 Å. The Bi(1)-Se(5) bond length is 3.29 Å. The Bi(1)-Se(6) bond length is 2.84 Å. There is one shorter (2.83 Å) and one longer (3.41 Å) Bi(1)-Se(1) bond length. There is one shorter (2.97 Å) and one longer (3.36 Å) Bi(1)-Se(3) 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 Se(1), one Se(3), and one Se(5) atom. The P(1)-P(2) bond length is 2.24 Å. The P(1)-Se(1) bond length is 2.23 Å. The P(1)-Se(3) bond length is 2.21 Å. The P(1)-Se(5) bond length is 2.17 Å. In the second P site, P(2) is bonded in a distorted tetrahedral geometry to one P(1), one Se(2), one Se(4), and one Se(6) atom. The P(2)-Se(2) bond length is 2.13 Å. The P(2)-Se(4) bond length is 2.18 Å. The P(2)-Se(6) bond length is 2.22 Å. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted water-like geometry to two equivalent Bi(1) and one P(1) atom. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to three equivalent K(1) and one P(2) atom. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to one K(1), two equivalent Bi(1), and one P(1) atom. In the fourth Se site, Se(4) 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 fifth Se site, Se(5) is bonded in a 4-coordinate geometry to two equivalent K(1), one Bi(1), and one P(1) atom. In the sixth Se site, Se(6) is bonded in a distorted T-shaped geometry to one K(1), one Bi(1), and one P(2) atom.