Rb3PS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(3) atoms. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(3), and three 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 Rb(1), four equivalent Rb(2), and one P(1) atom to form edge-sharing SRb5P octahedra. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Rb(1), three equivalent Rb(2), and one P(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Rb(1), four equivalent Rb(2), and one P(1) atom.
Rb3PS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(3) atoms. The Rb(1)-S(1) bond length is 3.31 Å. Both Rb(1)-S(2) bond lengths are 3.50 Å. There is one shorter (3.43 Å) and one longer (3.44 Å) Rb(1)-S(3) bond length. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms. There is one shorter (3.30 Å) and one longer (3.32 Å) Rb(2)-S(1) bond length. There is one shorter (3.46 Å) and one longer (3.51 Å) Rb(2)-S(3) bond length. There are a spread of Rb(2)-S(2) bond distances ranging from 3.42-3.44 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 2.04 Å. The P(1)-S(3) bond length is 2.06 Å. Both P(1)-S(2) bond lengths are 2.04 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Rb(1), four equivalent Rb(2), and one P(1) atom to form edge-sharing SRb5P octahedra. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Rb(1), three equivalent Rb(2), and one P(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Rb(1), four equivalent Rb(2), and one P(1) atom.