Rb2WS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), and four equivalent S(2) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to two equivalent S(3), three equivalent S(1), and four equivalent S(2) atoms. W(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 in a 6-coordinate geometry to two equivalent Rb(1), three equivalent Rb(2), and one W(1) atom. In the second S site, S(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one W(1) atom to form a mixture of distorted corner, edge, and face-sharing SRb4W trigonal bipyramids. In the third S site, S(3) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one W(1) atom to form a mixture of distorted corner and edge-sharing SRb4W square pyramids.
Rb2WS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), and four equivalent S(2) atoms. There is one shorter (3.61 Å) and one longer (3.84 Å) Rb(1)-S(1) bond length. Both Rb(1)-S(3) bond lengths are 3.59 Å. There are two shorter (3.58 Å) and two longer (3.60 Å) Rb(1)-S(2) bond lengths. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to two equivalent S(3), three equivalent S(1), and four equivalent S(2) atoms. There is one shorter (3.29 Å) and one longer (3.38 Å) Rb(2)-S(3) bond length. There is one shorter (3.51 Å) and two longer (3.64 Å) Rb(2)-S(1) bond lengths. There are two shorter (3.45 Å) and two longer (3.55 Å) Rb(2)-S(2) bond lengths. W(1) is bonded in a tetrahedral geometry to one S(1), one S(3), and two equivalent S(2) atoms. The W(1)-S(1) bond length is 2.20 Å. The W(1)-S(3) bond length is 2.20 Å. Both W(1)-S(2) bond lengths are 2.19 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Rb(1), three equivalent Rb(2), and one W(1) atom. In the second S site, S(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one W(1) atom to form a mixture of distorted corner, edge, and face-sharing SRb4W trigonal bipyramids. In the third S site, S(3) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one W(1) atom to form a mixture of distorted corner and edge-sharing SRb4W square pyramids.