Cs2AuPS4 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(1), four equivalent S(2), and four equivalent S(3) atoms. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to one S(3) and three equivalent S(1) atoms. Au(1) is bonded in a linear geometry to two equivalent S(2) atoms. P(1) is bonded in a tetrahedral geometry to one S(1), one S(3), and two equivalent S(2) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Cs(1), three equivalent Cs(2), and one P(1) atom to form distorted SCs4P trigonal bipyramids that share corners with two equivalent S(3)Cs5P octahedra, corners with two equivalent S(1)Cs4P trigonal bipyramids, edges with three equivalent S(3)Cs5P octahedra, and edges with two equivalent S(1)Cs4P trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-57°. In the second S site, S(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1), one Au(1), and one P(1) atom. In the third S site, S(3) is bonded to one Cs(2), four equivalent Cs(1), and one P(1) atom to form distorted SCs5P octahedra that share corners with four equivalent S(3)Cs5P octahedra, corners with two equivalent S(1)Cs4P trigonal bipyramids, edges with four equivalent S(3)Cs5P octahedra, and edges with three equivalent S(1)Cs4P trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-26°.
Cs2AuPS4 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(1), four equivalent S(2), and four equivalent S(3) atoms. The Cs(1)-S(1) bond length is 3.52 Å. There are two shorter (3.71 Å) and two longer (3.84 Å) Cs(1)-S(2) bond lengths. There are a spread of Cs(1)-S(3) bond distances ranging from 3.57-3.74 Å. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to one S(3) and three equivalent S(1) atoms. The Cs(2)-S(3) bond length is 3.78 Å. There is one shorter (3.59 Å) and two longer (3.68 Å) Cs(2)-S(1) bond lengths. Au(1) is bonded in a linear geometry to two equivalent S(2) atoms. Both Au(1)-S(2) bond lengths are 2.32 Å. P(1) is bonded in a tetrahedral geometry to one S(1), one S(3), and two equivalent S(2) atoms. The P(1)-S(1) bond length is 2.02 Å. The P(1)-S(3) bond length is 2.03 Å. Both P(1)-S(2) bond lengths are 2.11 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Cs(1), three equivalent Cs(2), and one P(1) atom to form distorted SCs4P trigonal bipyramids that share corners with two equivalent S(3)Cs5P octahedra, corners with two equivalent S(1)Cs4P trigonal bipyramids, edges with three equivalent S(3)Cs5P octahedra, and edges with two equivalent S(1)Cs4P trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-57°. In the second S site, S(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1), one Au(1), and one P(1) atom. In the third S site, S(3) is bonded to one Cs(2), four equivalent Cs(1), and one P(1) atom to form distorted SCs5P octahedra that share corners with four equivalent S(3)Cs5P octahedra, corners with two equivalent S(1)Cs4P trigonal bipyramids, edges with four equivalent S(3)Cs5P octahedra, and edges with three equivalent S(1)Cs4P trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-26°.