KSb(PSe3)2 crystallizes in the monoclinic P2_1 space group. K(1) is bonded in a 9-coordinate geometry to one Se(1), one Se(4), two equivalent Se(2), two equivalent Se(6), and three equivalent Se(3) atoms. Sb(1) is bonded in a 5-coordinate geometry to one Se(1), one Se(2), one Se(4), one Se(5), and one Se(6) atom. 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(2), one Se(3), and one Se(4) atom. In the second P site, P(2) is bonded in a distorted tetrahedral geometry to one P(1), one Se(1), one Se(5), and one Se(6) atom. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded in a 3-coordinate geometry to one K(1), one Sb(1), and one P(2) atom. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to two equivalent K(1), one Sb(1), and one P(1) atom. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to three equivalent K(1) and one P(1) atom. In the fourth Se site, Se(4) is bonded in a distorted L-shaped geometry to one K(1), one Sb(1), and one P(1) atom. In the fifth Se site, Se(5) is bonded in a water-like geometry to one Sb(1) and one P(2) atom. In the sixth Se site, Se(6) is bonded in a 4-coordinate geometry to two equivalent K(1), one Sb(1), and one P(2) atom.
KSb(PSe3)2 crystallizes in the monoclinic P2_1 space group. K(1) is bonded in a 9-coordinate geometry to one Se(1), one Se(4), two equivalent Se(2), two equivalent Se(6), and three equivalent Se(3) atoms. The K(1)-Se(1) bond length is 3.73 Å. The K(1)-Se(4) bond length is 3.87 Å. There is one shorter (3.48 Å) and one longer (3.54 Å) K(1)-Se(2) bond length. There is one shorter (3.63 Å) and one longer (3.66 Å) K(1)-Se(6) bond length. There are a spread of K(1)-Se(3) bond distances ranging from 3.47-3.69 Å. Sb(1) is bonded in a 5-coordinate geometry to one Se(1), one Se(2), one Se(4), one Se(5), and one Se(6) atom. The Sb(1)-Se(1) bond length is 2.82 Å. The Sb(1)-Se(2) bond length is 3.04 Å. The Sb(1)-Se(4) bond length is 2.73 Å. The Sb(1)-Se(5) bond length is 2.69 Å. The Sb(1)-Se(6) bond length is 3.24 Å. 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(2), one Se(3), and one Se(4) atom. The P(1)-P(2) bond length is 2.28 Å. The P(1)-Se(2) bond length is 2.20 Å. The P(1)-Se(3) bond length is 2.15 Å. The P(1)-Se(4) bond length is 2.24 Å. In the second P site, P(2) is bonded in a distorted tetrahedral geometry to one P(1), one Se(1), one Se(5), and one Se(6) atom. The P(2)-Se(1) bond length is 2.24 Å. The P(2)-Se(5) bond length is 2.28 Å. The P(2)-Se(6) bond length is 2.19 Å. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded in a 3-coordinate geometry to one K(1), one Sb(1), and one P(2) atom. In the second Se site, Se(2) is bonded in a 4-coordinate geometry to two equivalent K(1), one Sb(1), and one P(1) atom. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to three equivalent K(1) and one P(1) atom. In the fourth Se site, Se(4) is bonded in a distorted L-shaped geometry to one K(1), one Sb(1), and one P(1) atom. In the fifth Se site, Se(5) is bonded in a water-like geometry to one Sb(1) and one P(2) atom. In the sixth Se site, Se(6) is bonded in a 4-coordinate geometry to two equivalent K(1), one Sb(1), and one P(2) atom.