K3PS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and four equivalent S(3) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. P(1) is bonded in a tetrahedral geometry to one S(1), one S(2), and two equivalent S(3) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to one K(1), four equivalent K(2), and one P(1) atom to form edge-sharing SK5P octahedra. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent K(1), four equivalent K(2), and one P(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent K(1), three equivalent K(2), and one P(1) atom.
K3PS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and four equivalent S(3) atoms. The K(1)-S(1) bond length is 3.12 Å. There is one shorter (3.32 Å) and one longer (3.37 Å) K(1)-S(2) bond length. There are two shorter (3.30 Å) and two longer (3.74 Å) K(1)-S(3) bond lengths. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. There is one shorter (3.15 Å) and one longer (3.20 Å) K(2)-S(1) bond length. There is one shorter (3.29 Å) and one longer (3.43 Å) K(2)-S(2) bond length. There are a spread of K(2)-S(3) bond distances ranging from 3.25-3.39 Å. P(1) is bonded in a tetrahedral geometry to one S(1), one S(2), and two equivalent S(3) atoms. The P(1)-S(1) bond length is 2.04 Å. The P(1)-S(2) bond length is 2.06 Å. Both P(1)-S(3) bond lengths are 2.04 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one K(1), four equivalent K(2), and one P(1) atom to form edge-sharing SK5P octahedra. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent K(1), four equivalent K(2), and one P(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent K(1), three equivalent K(2), and one P(1) atom.