KIn(PSe3)2 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 6-coordinate geometry to one Se(1), one Se(5), two equivalent Se(4), and two equivalent Se(6) atoms. In(1) is bonded to one Se(1), one Se(5), two equivalent Se(2), and two equivalent Se(3) atoms to form InSe6 octahedra that share corners with three equivalent P(1)PSe3 tetrahedra, corners with three equivalent P(2)PSe3 tetrahedra, and edges with two equivalent In(1)Se6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one P(2), one Se(2), one Se(4), and one Se(5) atom to form distorted PPSe3 tetrahedra that share corners with three equivalent In(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 73-82°. In the second P site, P(2) is bonded to one P(1), one Se(1), one Se(3), and one Se(6) atom to form distorted PPSe3 tetrahedra that share corners with three equivalent In(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 73-82°. There are six inequivalent Se sites. In the first Se site, Se(5) is bonded in a 3-coordinate geometry to one K(1), one In(1), and one P(1) atom. In the second Se site, Se(6) is bonded in a 3-coordinate geometry to two equivalent K(1) and one P(2) atom. In the third Se site, Se(1) is bonded in a 3-coordinate geometry to one K(1), one In(1), and one P(2) atom. In the fourth Se site, Se(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent In(1) and one P(1) atom. In the fifth Se site, Se(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent In(1) and one P(2) atom. In the sixth Se site, Se(4) is bonded in a 3-coordinate geometry to two equivalent K(1) and one P(1) atom.
KIn(PSe3)2 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 6-coordinate geometry to one Se(1), one Se(5), two equivalent Se(4), and two equivalent Se(6) atoms. The K(1)-Se(1) bond length is 3.50 Å. The K(1)-Se(5) bond length is 3.55 Å. There is one shorter (3.36 Å) and one longer (3.71 Å) K(1)-Se(4) bond length. There is one shorter (3.36 Å) and one longer (3.88 Å) K(1)-Se(6) bond length. In(1) is bonded to one Se(1), one Se(5), two equivalent Se(2), and two equivalent Se(3) atoms to form InSe6 octahedra that share corners with three equivalent P(1)PSe3 tetrahedra, corners with three equivalent P(2)PSe3 tetrahedra, and edges with two equivalent In(1)Se6 octahedra. The In(1)-Se(1) bond length is 2.75 Å. The In(1)-Se(5) bond length is 2.75 Å. There is one shorter (2.82 Å) and one longer (2.90 Å) In(1)-Se(2) bond length. There is one shorter (2.81 Å) and one longer (2.90 Å) In(1)-Se(3) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one P(2), one Se(2), one Se(4), and one Se(5) atom to form distorted PPSe3 tetrahedra that share corners with three equivalent In(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 73-82°. The P(1)-P(2) bond length is 2.28 Å. The P(1)-Se(2) bond length is 2.26 Å. The P(1)-Se(4) bond length is 2.16 Å. The P(1)-Se(5) bond length is 2.22 Å. In the second P site, P(2) is bonded to one P(1), one Se(1), one Se(3), and one Se(6) atom to form distorted PPSe3 tetrahedra that share corners with three equivalent In(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 73-82°. The P(2)-Se(1) bond length is 2.22 Å. The P(2)-Se(3) bond length is 2.27 Å. The P(2)-Se(6) bond length is 2.15 Å. There are six inequivalent Se sites. In the first Se site, Se(5) is bonded in a 3-coordinate geometry to one K(1), one In(1), and one P(1) atom. In the second Se site, Se(6) is bonded in a 3-coordinate geometry to two equivalent K(1) and one P(2) atom. In the third Se site, Se(1) is bonded in a 3-coordinate geometry to one K(1), one In(1), and one P(2) atom. In the fourth Se site, Se(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent In(1) and one P(1) atom. In the fifth Se site, Se(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent In(1) and one P(2) atom. In the sixth Se site, Se(4) is bonded in a 3-coordinate geometry to two equivalent K(1) and one P(1) atom.