K4Eu(PS4)2 crystallizes in the triclinic P1 space group. There are eight inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one S(11), one S(13), one S(14), one S(15), one S(3), one S(5), one S(8), and one S(9) atom. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(10), one S(12), one S(15), one S(16), one S(6), and one S(7) atom. In the third K site, K(3) is bonded in a 8-coordinate geometry to one S(11), one S(12), one S(13), one S(2), one S(3), one S(4), one S(5), and one S(7) atom. In the fourth K site, K(4) is bonded in a 6-coordinate geometry to one S(1), one S(10), one S(15), one S(16), one S(7), and one S(8) atom. In the fifth K site, K(5) is bonded in a 8-coordinate geometry to one S(10), one S(11), one S(14), one S(2), one S(3), one S(4), one S(6), and one S(9) atom. In the sixth K site, K(6) is bonded in a 6-coordinate geometry to one S(1), one S(10), one S(15), one S(16), one S(7), and one S(8) atom. In the seventh K site, K(7) is bonded in a 6-coordinate geometry to one S(10), one S(12), one S(15), one S(16), one S(6), and one S(7) atom. In the eighth K site, K(8) is bonded in a 8-coordinate geometry to one S(1), one S(13), one S(14), one S(16), one S(2), one S(4), one S(5), and one S(9) atom. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded to one S(1), one S(11), one S(12), one S(14), one S(4), one S(5), one S(6), and one S(8) atom to form distorted EuS8 hexagonal bipyramids that share edges with two equivalent Eu(2)S8 hexagonal bipyramids,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra,  an edgeedge with one P(3)S4 tetrahedra, and  an edgeedge with one P(4)S4 tetrahedra. In the second Eu site, Eu(2) is bonded to one S(1), one S(12), one S(13), one S(2), one S(3), one S(6), one S(8), and one S(9) atom to form distorted EuS8 hexagonal bipyramids that share edges with two equivalent Eu(1)S8 hexagonal bipyramids,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra,  an edgeedge with one P(3)S4 tetrahedra, and  an edgeedge with one P(4)S4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one S(11), one S(12), one S(16), and one S(3) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. In the second P site, P(2) is bonded to one S(10), one S(13), one S(5), and one S(8) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. In the third P site, P(3) is bonded to one S(15), one S(2), one S(4), and one S(6) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. In the fourth P site, P(4) is bonded to one S(1), one S(14), one S(7), and one S(9) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one K(4), one K(6), one K(8), one Eu(1), one Eu(2), and one P(4) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to one K(3), one K(5), one K(8), one Eu(2), and one P(3) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one K(3), one K(5), one Eu(2), and one P(1) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one K(3), one K(5), one K(8), one Eu(1), and one P(3) atom. In the fifth S site, S(5) is bonded in a 1-coordinate geometry to one K(1), one K(3), one K(8), one Eu(1), and one P(2) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one K(2), one K(5), one K(7), one Eu(1), one Eu(2), and one P(3) atom. In the seventh S site, S(7) is bonded to one K(2), one K(3), one K(4), one K(6), one K(7), and one P(4) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one K(1), one K(4), one K(6), one Eu(1), one Eu(2), and one P(2) atom. In the ninth S site, S(9) is bonded in a 5-coordinate geometry to one K(1), one K(5), one K(8), one Eu(2), and one P(4) atom. In the tenth S site, S(10) is bonded to one K(2), one K(4), one K(5), one K(6), one K(7), and one P(2) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to one K(1), one K(3), one K(5), one Eu(1), and one P(1) atom. In the twelfth S site, S(12) is bonded in a 6-coordinate geometry to one K(2), one K(3), one K(7), one Eu(1), one Eu(2), and one P(1) atom. In the thirteenth S site, S(13) is bonded in a 1-coordinate geometry to one K(1), one K(3), one K(8), one Eu(2), and one P(2) atom. In the fourteenth S site, S(14) is bonded in a 1-coordinate geometry to one K(1), one K(5), one K(8), one Eu(1), and one P(4) atom. In the fifteenth S site, S(15) is bonded to one K(1), one K(2), one K(4), one K(6), one K(7), and one P(3) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 3-14°. In the sixteenth S site, S(16) is bonded to one K(2), one K(4), one K(6), one K(7), one K(8), and one P(1) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 3-14°.
K4Eu(PS4)2 crystallizes in the triclinic P1 space group. There are eight inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one S(11), one S(13), one S(14), one S(15), one S(3), one S(5), one S(8), and one S(9) atom. The K(1)-S(11) bond length is 3.50 Å. The K(1)-S(13) bond length is 3.34 Å. The K(1)-S(14) bond length is 3.34 Å. The K(1)-S(15) bond length is 3.47 Å. The K(1)-S(3) bond length is 3.52 Å. The K(1)-S(5) bond length is 3.34 Å. The K(1)-S(8) bond length is 3.21 Å. The K(1)-S(9) bond length is 3.35 Å. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(10), one S(12), one S(15), one S(16), one S(6), and one S(7) atom. The K(2)-S(10) bond length is 3.36 Å. The K(2)-S(12) bond length is 3.58 Å. The K(2)-S(15) bond length is 3.26 Å. The K(2)-S(16) bond length is 3.32 Å. The K(2)-S(6) bond length is 3.53 Å. The K(2)-S(7) bond length is 3.35 Å. In the third K site, K(3) is bonded in a 8-coordinate geometry to one S(11), one S(12), one S(13), one S(2), one S(3), one S(4), one S(5), and one S(7) atom. The K(3)-S(11) bond length is 3.37 Å. The K(3)-S(12) bond length is 3.15 Å. The K(3)-S(13) bond length is 3.56 Å. The K(3)-S(2) bond length is 3.32 Å. The K(3)-S(3) bond length is 3.38 Å. The K(3)-S(4) bond length is 3.34 Å. The K(3)-S(5) bond length is 3.52 Å. The K(3)-S(7) bond length is 3.42 Å. In the fourth K site, K(4) is bonded in a 6-coordinate geometry to one S(1), one S(10), one S(15), one S(16), one S(7), and one S(8) atom. The K(4)-S(1) bond length is 3.53 Å. The K(4)-S(10) bond length is 3.30 Å. The K(4)-S(15) bond length is 3.34 Å. The K(4)-S(16) bond length is 3.39 Å. The K(4)-S(7) bond length is 3.32 Å. The K(4)-S(8) bond length is 3.52 Å. In the fifth K site, K(5) is bonded in a 8-coordinate geometry to one S(10), one S(11), one S(14), one S(2), one S(3), one S(4), one S(6), and one S(9) atom. The K(5)-S(10) bond length is 3.53 Å. The K(5)-S(11) bond length is 3.34 Å. The K(5)-S(14) bond length is 3.50 Å. The K(5)-S(2) bond length is 3.34 Å. The K(5)-S(3) bond length is 3.32 Å. The K(5)-S(4) bond length is 3.34 Å. The K(5)-S(6) bond length is 3.19 Å. The K(5)-S(9) bond length is 3.49 Å. In the sixth K site, K(6) is bonded in a 6-coordinate geometry to one S(1), one S(10), one S(15), one S(16), one S(7), and one S(8) atom. The K(6)-S(1) bond length is 3.48 Å. The K(6)-S(10) bond length is 3.28 Å. The K(6)-S(15) bond length is 3.40 Å. The K(6)-S(16) bond length is 3.38 Å. The K(6)-S(7) bond length is 3.26 Å. The K(6)-S(8) bond length is 3.53 Å. In the seventh K site, K(7) is bonded in a 6-coordinate geometry to one S(10), one S(12), one S(15), one S(16), one S(6), and one S(7) atom. The K(7)-S(10) bond length is 3.35 Å. The K(7)-S(12) bond length is 3.58 Å. The K(7)-S(15) bond length is 3.27 Å. The K(7)-S(16) bond length is 3.30 Å. The K(7)-S(6) bond length is 3.48 Å. The K(7)-S(7) bond length is 3.41 Å. In the eighth K site, K(8) is bonded in a 8-coordinate geometry to one S(1), one S(13), one S(14), one S(16), one S(2), one S(4), one S(5), and one S(9) atom. The K(8)-S(1) bond length is 3.15 Å. The K(8)-S(13) bond length is 3.30 Å. The K(8)-S(14) bond length is 3.38 Å. The K(8)-S(16) bond length is 3.46 Å. The K(8)-S(2) bond length is 3.52 Å. The K(8)-S(4) bond length is 3.53 Å. The K(8)-S(5) bond length is 3.36 Å. The K(8)-S(9) bond length is 3.39 Å. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded to one S(1), one S(11), one S(12), one S(14), one S(4), one S(5), one S(6), and one S(8) atom to form distorted EuS8 hexagonal bipyramids that share edges with two equivalent Eu(2)S8 hexagonal bipyramids,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra,  an edgeedge with one P(3)S4 tetrahedra, and  an edgeedge with one P(4)S4 tetrahedra. The Eu(1)-S(1) bond length is 3.13 Å. The Eu(1)-S(11) bond length is 3.14 Å. The Eu(1)-S(12) bond length is 3.14 Å. The Eu(1)-S(14) bond length is 3.14 Å. The Eu(1)-S(4) bond length is 3.14 Å. The Eu(1)-S(5) bond length is 3.11 Å. The Eu(1)-S(6) bond length is 3.16 Å. The Eu(1)-S(8) bond length is 3.13 Å. In the second Eu site, Eu(2) is bonded to one S(1), one S(12), one S(13), one S(2), one S(3), one S(6), one S(8), and one S(9) atom to form distorted EuS8 hexagonal bipyramids that share edges with two equivalent Eu(1)S8 hexagonal bipyramids,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra,  an edgeedge with one P(3)S4 tetrahedra, and  an edgeedge with one P(4)S4 tetrahedra. The Eu(2)-S(1) bond length is 3.15 Å. The Eu(2)-S(12) bond length is 3.13 Å. The Eu(2)-S(13) bond length is 3.15 Å. The Eu(2)-S(2) bond length is 3.17 Å. The Eu(2)-S(3) bond length is 3.11 Å. The Eu(2)-S(6) bond length is 3.13 Å. The Eu(2)-S(8) bond length is 3.13 Å. The Eu(2)-S(9) bond length is 3.08 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one S(11), one S(12), one S(16), and one S(3) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. The P(1)-S(11) bond length is 2.06 Å. The P(1)-S(12) bond length is 2.07 Å. The P(1)-S(16) bond length is 2.04 Å. The P(1)-S(3) bond length is 2.06 Å. In the second P site, P(2) is bonded to one S(10), one S(13), one S(5), and one S(8) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. The P(2)-S(10) bond length is 2.04 Å. The P(2)-S(13) bond length is 2.05 Å. The P(2)-S(5) bond length is 2.06 Å. The P(2)-S(8) bond length is 2.07 Å. In the third P site, P(3) is bonded to one S(15), one S(2), one S(4), and one S(6) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. The P(3)-S(15) bond length is 2.04 Å. The P(3)-S(2) bond length is 2.05 Å. The P(3)-S(4) bond length is 2.05 Å. The P(3)-S(6) bond length is 2.08 Å. In the fourth P site, P(4) is bonded to one S(1), one S(14), one S(7), and one S(9) atom to form PS4 tetrahedra that share  an edgeedge with one Eu(1)S8 hexagonal bipyramid and  an edgeedge with one Eu(2)S8 hexagonal bipyramid. The P(4)-S(1) bond length is 2.08 Å. The P(4)-S(14) bond length is 2.06 Å. The P(4)-S(7) bond length is 2.04 Å. The P(4)-S(9) bond length is 2.05 Å. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one K(4), one K(6), one K(8), one Eu(1), one Eu(2), and one P(4) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to one K(3), one K(5), one K(8), one Eu(2), and one P(3) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one K(3), one K(5), one Eu(2), and one P(1) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one K(3), one K(5), one K(8), one Eu(1), and one P(3) atom. In the fifth S site, S(5) is bonded in a 1-coordinate geometry to one K(1), one K(3), one K(8), one Eu(1), and one P(2) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one K(2), one K(5), one K(7), one Eu(1), one Eu(2), and one P(3) atom. In the seventh S site, S(7) is bonded to one K(2), one K(3), one K(4), one K(6), one K(7), and one P(4) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one K(1), one K(4), one K(6), one Eu(1), one Eu(2), and one P(2) atom. In the ninth S site, S(9) is bonded in a 5-coordinate geometry to one K(1), one K(5), one K(8), one Eu(2), and one P(4) atom. In the tenth S site, S(10) is bonded to one K(2), one K(4), one K(5), one K(6), one K(7), and one P(2) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to one K(1), one K(3), one K(5), one Eu(1), and one P(1) atom. In the twelfth S site, S(12) is bonded in a 6-coordinate geometry to one K(2), one K(3), one K(7), one Eu(1), one Eu(2), and one P(1) atom. In the thirteenth S site, S(13) is bonded in a 1-coordinate geometry to one K(1), one K(3), one K(8), one Eu(2), and one P(2) atom. In the fourteenth S site, S(14) is bonded in a 1-coordinate geometry to one K(1), one K(5), one K(8), one Eu(1), and one P(4) atom. In the fifteenth S site, S(15) is bonded to one K(1), one K(2), one K(4), one K(6), one K(7), and one P(3) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 3-14°. In the sixteenth S site, S(16) is bonded to one K(2), one K(4), one K(6), one K(7), one K(8), and one P(1) atom to form a mixture of distorted edge and corner-sharing SK5P octahedra. The corner-sharing octahedral tilt angles range from 3-14°.