Ba3(PS4)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one S(8), two equivalent S(7), three equivalent S(1), and three equivalent S(2) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(6), one S(7), two equivalent S(5), and two equivalent S(8) atoms. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one S(5), two equivalent S(6), three equivalent S(3), and three equivalent S(4) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one S(3), one S(4), one S(6), and one S(8) atom. In the second P site, P(2) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(5), and one S(7) atom. There are eight inequivalent S sites. In the first S site, S(6) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(3), and one P(1) atom. In the second S site, S(7) is bonded in a 1-coordinate geometry to one Ba(2), two equivalent Ba(1), and one P(2) atom. In the third S site, S(8) is bonded in a 4-coordinate geometry to one Ba(1), two equivalent Ba(2), and one P(1) atom. In the fourth S site, S(1) is bonded in a 5-coordinate geometry to one Ba(2), three equivalent Ba(1), and one P(2) atom. In the fifth S site, S(2) is bonded to one Ba(2), three equivalent Ba(1), and one P(2) atom to form a mixture of distorted corner and edge-sharing SBa4P square pyramids. In the sixth S site, S(3) is bonded to one Ba(2), three equivalent Ba(3), and one P(1) atom to form a mixture of distorted corner and edge-sharing SBa4P square pyramids. In the seventh S site, S(4) is bonded in a 1-coordinate geometry to one Ba(2), three equivalent Ba(3), and one P(1) atom. In the eighth S site, S(5) is bonded in a 4-coordinate geometry to one Ba(3), two equivalent Ba(2), and one P(2) atom.
Ba3(PS4)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one S(8), two equivalent S(7), three equivalent S(1), and three equivalent S(2) atoms. The Ba(1)-S(8) bond length is 3.21 Å. There is one shorter (3.29 Å) and one longer (3.59 Å) Ba(1)-S(7) bond length. There are two shorter (3.34 Å) and one longer (3.56 Å) Ba(1)-S(1) bond length. There are a spread of Ba(1)-S(2) bond distances ranging from 3.32-3.36 Å. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(6), one S(7), two equivalent S(5), and two equivalent S(8) atoms. The Ba(2)-S(1) bond length is 3.39 Å. The Ba(2)-S(2) bond length is 3.37 Å. The Ba(2)-S(3) bond length is 3.29 Å. The Ba(2)-S(4) bond length is 3.65 Å. The Ba(2)-S(6) bond length is 3.27 Å. The Ba(2)-S(7) bond length is 3.32 Å. There is one shorter (3.33 Å) and one longer (3.47 Å) Ba(2)-S(5) bond length. There is one shorter (3.38 Å) and one longer (3.57 Å) Ba(2)-S(8) bond length. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one S(5), two equivalent S(6), three equivalent S(3), and three equivalent S(4) atoms. The Ba(3)-S(5) bond length is 3.21 Å. There is one shorter (3.26 Å) and one longer (3.61 Å) Ba(3)-S(6) bond length. There are a spread of Ba(3)-S(3) bond distances ranging from 3.37-3.40 Å. There are a spread of Ba(3)-S(4) bond distances ranging from 3.28-3.52 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one S(3), one S(4), one S(6), and one S(8) atom. The P(1)-S(3) bond length is 2.05 Å. The P(1)-S(4) bond length is 2.04 Å. The P(1)-S(6) bond length is 2.04 Å. The P(1)-S(8) bond length is 2.02 Å. In the second P site, P(2) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(5), and one S(7) atom. The P(2)-S(1) bond length is 2.04 Å. The P(2)-S(2) bond length is 2.05 Å. The P(2)-S(5) bond length is 2.02 Å. The P(2)-S(7) bond length is 2.03 Å. There are eight inequivalent S sites. In the first S site, S(6) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(3), and one P(1) atom. In the second S site, S(7) is bonded in a 1-coordinate geometry to one Ba(2), two equivalent Ba(1), and one P(2) atom. In the third S site, S(8) is bonded in a 4-coordinate geometry to one Ba(1), two equivalent Ba(2), and one P(1) atom. In the fourth S site, S(1) is bonded in a 5-coordinate geometry to one Ba(2), three equivalent Ba(1), and one P(2) atom. In the fifth S site, S(2) is bonded to one Ba(2), three equivalent Ba(1), and one P(2) atom to form a mixture of distorted corner and edge-sharing SBa4P square pyramids. In the sixth S site, S(3) is bonded to one Ba(2), three equivalent Ba(3), and one P(1) atom to form a mixture of distorted corner and edge-sharing SBa4P square pyramids. In the seventh S site, S(4) is bonded in a 1-coordinate geometry to one Ba(2), three equivalent Ba(3), and one P(1) atom. In the eighth S site, S(5) is bonded in a 4-coordinate geometry to one Ba(3), two equivalent Ba(2), and one P(2) atom.