RbBaPS4 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(2), and four equivalent S(1) atoms. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(2), three equivalent S(3), and four equivalent S(1) atoms. P(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 1-coordinate geometry to two equivalent Rb(1), two equivalent Ba(1), and one P(1) atom. In the second S site, S(2) is bonded to two equivalent Rb(1), two equivalent Ba(1), and one P(1) atom to form distorted corner-sharing SRb2Ba2P trigonal bipyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), three equivalent Ba(1), and one P(1) atom.
RbBaPS4 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(2), and four equivalent S(1) atoms. The Rb(1)-S(3) bond length is 3.53 Å. Both Rb(1)-S(2) bond lengths are 3.50 Å. There are two shorter (3.57 Å) and two longer (3.75 Å) Rb(1)-S(1) bond lengths. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(2), three equivalent S(3), and four equivalent S(1) atoms. There is one shorter (3.19 Å) and one longer (3.40 Å) Ba(1)-S(2) bond length. There is one shorter (3.30 Å) and two longer (3.51 Å) Ba(1)-S(3) bond lengths. There are two shorter (3.26 Å) and two longer (3.40 Å) Ba(1)-S(1) bond lengths. P(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. The P(1)-S(2) bond length is 2.06 Å. The P(1)-S(3) bond length is 2.07 Å. Both P(1)-S(1) bond lengths are 2.04 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 1-coordinate geometry to two equivalent Rb(1), two equivalent Ba(1), and one P(1) atom. In the second S site, S(2) is bonded to two equivalent Rb(1), two equivalent Ba(1), and one P(1) atom to form distorted corner-sharing SRb2Ba2P trigonal bipyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), three equivalent Ba(1), and one P(1) atom.