P4S9 is black P structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four P4S9 clusters. There are four inequivalent P sites. In the first P site, P(1) is bonded in a trigonal non-coplanar geometry to one S(2), one S(4), and one S(8) atom. In the second P site, P(2) is bonded to one S(1), one S(7), one S(8), and one S(9) atom to form corner-sharing PS4 tetrahedra. In the third P site, P(3) is bonded to one S(1), one S(4), one S(5), and one S(6) atom to form corner-sharing PS4 tetrahedra. In the fourth P site, P(4) is bonded to one S(2), one S(3), one S(5), and one S(7) atom to form corner-sharing PS4 tetrahedra. There are nine inequivalent S sites. In the first S site, S(5) is bonded in a water-like geometry to one P(3) and one P(4) atom. In the second S site, S(6) is bonded in a single-bond geometry to one P(3) atom. In the third S site, S(7) is bonded in a water-like geometry to one P(2) and one P(4) atom. In the fourth S site, S(8) is bonded in a water-like geometry to one P(1) and one P(2) atom. In the fifth S site, S(1) is bonded in a water-like geometry to one P(2) and one P(3) atom. In the sixth S site, S(9) is bonded in a single-bond geometry to one P(2) atom. In the seventh S site, S(2) is bonded in a water-like geometry to one P(1) and one P(4) atom. In the eighth S site, S(3) is bonded in a single-bond geometry to one P(4) atom. In the ninth S site, S(4) is bonded in a water-like geometry to one P(1) and one P(3) atom.
P4S9 is black P structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four P4S9 clusters. There are four inequivalent P sites. In the first P site, P(1) is bonded in a trigonal non-coplanar geometry to one S(2), one S(4), and one S(8) atom. The P(1)-S(2) bond length is 2.11 Å. The P(1)-S(4) bond length is 2.11 Å. The P(1)-S(8) bond length is 2.11 Å. In the second P site, P(2) is bonded to one S(1), one S(7), one S(8), and one S(9) atom to form corner-sharing PS4 tetrahedra. The P(2)-S(1) bond length is 2.10 Å. The P(2)-S(7) bond length is 2.10 Å. The P(2)-S(8) bond length is 2.08 Å. The P(2)-S(9) bond length is 1.91 Å. In the third P site, P(3) is bonded to one S(1), one S(4), one S(5), and one S(6) atom to form corner-sharing PS4 tetrahedra. The P(3)-S(1) bond length is 2.11 Å. The P(3)-S(4) bond length is 2.08 Å. The P(3)-S(5) bond length is 2.11 Å. The P(3)-S(6) bond length is 1.91 Å. In the fourth P site, P(4) is bonded to one S(2), one S(3), one S(5), and one S(7) atom to form corner-sharing PS4 tetrahedra. The P(4)-S(2) bond length is 2.09 Å. The P(4)-S(3) bond length is 1.92 Å. The P(4)-S(5) bond length is 2.10 Å. The P(4)-S(7) bond length is 2.10 Å. There are nine inequivalent S sites. In the first S site, S(5) is bonded in a water-like geometry to one P(3) and one P(4) atom. In the second S site, S(6) is bonded in a single-bond geometry to one P(3) atom. In the third S site, S(7) is bonded in a water-like geometry to one P(2) and one P(4) atom. In the fourth S site, S(8) is bonded in a water-like geometry to one P(1) and one P(2) atom. In the fifth S site, S(1) is bonded in a water-like geometry to one P(2) and one P(3) atom. In the sixth S site, S(9) is bonded in a single-bond geometry to one P(2) atom. In the seventh S site, S(2) is bonded in a water-like geometry to one P(1) and one P(4) atom. In the eighth S site, S(3) is bonded in a single-bond geometry to one P(4) atom. In the ninth S site, S(4) is bonded in a water-like geometry to one P(1) and one P(3) atom.