Rb2AuSbS4 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), and four equivalent S(2) atoms. In the second Rb site, Rb(2) is bonded in a 4-coordinate geometry to one S(2) and three equivalent S(3) atoms. Au(1) is bonded in a linear geometry to two equivalent S(1) atoms. Sb(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 3-coordinate geometry to one Rb(1), one Au(1), and one Sb(1) atom. In the second S site, S(2) is bonded to one Rb(2), four equivalent Rb(1), and one Sb(1) atom to form distorted SRb5Sb octahedra that share corners with four equivalent S(2)Rb5Sb octahedra, corners with two equivalent S(3)Rb4Sb trigonal bipyramids, edges with four equivalent S(2)Rb5Sb octahedra, and edges with three equivalent S(3)Rb4Sb trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-21°. In the third S site, S(3) is bonded to one Rb(1), three equivalent Rb(2), and one Sb(1) atom to form distorted SRb4Sb trigonal bipyramids that share corners with two equivalent S(2)Rb5Sb octahedra, corners with two equivalent S(3)Rb4Sb trigonal bipyramids, edges with three equivalent S(2)Rb5Sb octahedra, and edges with two equivalent S(3)Rb4Sb trigonal bipyramids. The corner-sharing octahedral tilt angles range from 11-60°.
Rb2AuSbS4 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), and four equivalent S(2) atoms. The Rb(1)-S(3) bond length is 3.38 Å. Both Rb(1)-S(1) bond lengths are 3.58 Å. There are a spread of Rb(1)-S(2) bond distances ranging from 3.51-3.76 Å. In the second Rb site, Rb(2) is bonded in a 4-coordinate geometry to one S(2) and three equivalent S(3) atoms. The Rb(2)-S(2) bond length is 3.52 Å. There is one shorter (3.45 Å) and two longer (3.71 Å) Rb(2)-S(3) bond lengths. Au(1) is bonded in a linear geometry to two equivalent S(1) atoms. Both Au(1)-S(1) bond lengths are 2.31 Å. Sb(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Sb(1)-S(2) bond length is 2.34 Å. The Sb(1)-S(3) bond length is 2.33 Å. Both Sb(1)-S(1) bond lengths are 2.41 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Rb(1), one Au(1), and one Sb(1) atom. In the second S site, S(2) is bonded to one Rb(2), four equivalent Rb(1), and one Sb(1) atom to form distorted SRb5Sb octahedra that share corners with four equivalent S(2)Rb5Sb octahedra, corners with two equivalent S(3)Rb4Sb trigonal bipyramids, edges with four equivalent S(2)Rb5Sb octahedra, and edges with three equivalent S(3)Rb4Sb trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-21°. In the third S site, S(3) is bonded to one Rb(1), three equivalent Rb(2), and one Sb(1) atom to form distorted SRb4Sb trigonal bipyramids that share corners with two equivalent S(2)Rb5Sb octahedra, corners with two equivalent S(3)Rb4Sb trigonal bipyramids, edges with three equivalent S(2)Rb5Sb octahedra, and edges with two equivalent S(3)Rb4Sb trigonal bipyramids. The corner-sharing octahedral tilt angles range from 11-60°.