K2Fe(PSe3)2 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to two equivalent Se(2), three equivalent Se(3), and four equivalent Se(1) atoms. Fe(1) is bonded in an octahedral geometry to two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. P(1) is bonded in a 4-coordinate geometry to one P(1), one Se(1), one Se(2), and one Se(3) atom. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a 3-coordinate geometry to four equivalent K(1), one Fe(1), and one P(1) atom. In the second Se site, Se(2) is bonded in a distorted see-saw-like geometry to two equivalent K(1), one Fe(1), and one P(1) atom. In the third Se site, Se(3) is bonded to three equivalent K(1), one Fe(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing SeK3FeP trigonal bipyramids.
K2Fe(PSe3)2 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to two equivalent Se(2), three equivalent Se(3), and four equivalent Se(1) atoms. There is one shorter (3.42 Å) and one longer (3.66 Å) K(1)-Se(2) bond length. There are a spread of K(1)-Se(3) bond distances ranging from 3.49-3.66 Å. There are a spread of K(1)-Se(1) bond distances ranging from 3.47-3.98 Å. Fe(1) is bonded in an octahedral geometry to two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. Both Fe(1)-Se(1) bond lengths are 2.77 Å. Both Fe(1)-Se(2) bond lengths are 2.65 Å. Both Fe(1)-Se(3) bond lengths are 2.62 Å. P(1) is bonded in a 4-coordinate geometry to one P(1), one Se(1), one Se(2), and one Se(3) atom. The P(1)-P(1) bond length is 2.26 Å. The P(1)-Se(1) bond length is 2.20 Å. The P(1)-Se(2) bond length is 2.20 Å. The P(1)-Se(3) bond length is 2.22 Å. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a 3-coordinate geometry to four equivalent K(1), one Fe(1), and one P(1) atom. In the second Se site, Se(2) is bonded in a distorted see-saw-like geometry to two equivalent K(1), one Fe(1), and one P(1) atom. In the third Se site, Se(3) is bonded to three equivalent K(1), one Fe(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing SeK3FeP trigonal bipyramids.