K8La(PS4)4 crystallizes in the orthorhombic I222 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(4), and four equivalent S(3) atoms. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent S(4) and four equivalent S(3) atoms. In the third K site, K(3) is bonded in a 8-coordinate geometry to one S(3), one S(4), three equivalent S(1), and three equivalent S(2) atoms. La(1) is bonded to four equivalent S(1) and four equivalent S(4) atoms to form distorted LaS8 hexagonal bipyramids that share edges with four equivalent P(1)S4 tetrahedra. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share  an edgeedge with one La(1)S8 hexagonal bipyramid. There are four inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one K(3), two equivalent K(1), two equivalent K(2), and one P(1) atom. In the second S site, S(4) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one La(1), and one P(1) atom. In the third S site, S(1) is bonded in a 5-coordinate geometry to three equivalent K(3), one La(1), and one P(1) atom. In the fourth S site, S(2) is bonded in a 5-coordinate geometry to one K(1), three equivalent K(3), and one P(1) atom.
K8La(PS4)4 crystallizes in the orthorhombic I222 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(4), and four equivalent S(3) atoms. Both K(1)-S(2) bond lengths are 3.69 Å. Both K(1)-S(4) bond lengths are 3.44 Å. There are two shorter (3.28 Å) and two longer (3.40 Å) K(1)-S(3) bond lengths. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent S(4) and four equivalent S(3) atoms. Both K(2)-S(4) bond lengths are 3.52 Å. All K(2)-S(3) bond lengths are 3.35 Å. In the third K site, K(3) is bonded in a 8-coordinate geometry to one S(3), one S(4), three equivalent S(1), and three equivalent S(2) atoms. The K(3)-S(3) bond length is 3.53 Å. The K(3)-S(4) bond length is 3.17 Å. There are a spread of K(3)-S(1) bond distances ranging from 3.36-3.51 Å. There are a spread of K(3)-S(2) bond distances ranging from 3.28-3.43 Å. La(1) is bonded to four equivalent S(1) and four equivalent S(4) atoms to form distorted LaS8 hexagonal bipyramids that share edges with four equivalent P(1)S4 tetrahedra. All La(1)-S(1) bond lengths are 3.07 Å. All La(1)-S(4) bond lengths are 3.03 Å. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share  an edgeedge with one La(1)S8 hexagonal bipyramid. The P(1)-S(1) bond length is 2.06 Å. The P(1)-S(2) bond length is 2.04 Å. The P(1)-S(3) bond length is 2.05 Å. The P(1)-S(4) bond length is 2.05 Å. There are four inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one K(3), two equivalent K(1), two equivalent K(2), and one P(1) atom. In the second S site, S(4) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one La(1), and one P(1) atom. In the third S site, S(1) is bonded in a 5-coordinate geometry to three equivalent K(3), one La(1), and one P(1) atom. In the fourth S site, S(2) is bonded in a 5-coordinate geometry to one K(1), three equivalent K(3), and one P(1) atom.