Rb2S5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one S(3), one S(5), two equivalent S(2), two equivalent S(4), and three equivalent S(1) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Rb(2), three equivalent Rb(1), and one S(2) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one S(1), and one S(5) atom. In the third S site, S(3) is bonded to one Rb(1), four equivalent Rb(2), and one S(4) atom to form a mixture of distorted edge and corner-sharing SRb5S pentagonal pyramids. In the fourth S site, S(4) is bonded in a distorted pentagonal planar geometry to one Rb(2), two equivalent Rb(1), one S(3), and one S(5) atom. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one S(2), and one S(4) atom.
Rb2S5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one S(3), one S(5), two equivalent S(2), two equivalent S(4), and three equivalent S(1) atoms. The Rb(1)-S(3) bond length is 3.44 Å. The Rb(1)-S(5) bond length is 3.56 Å. There is one shorter (3.64 Å) and one longer (3.69 Å) Rb(1)-S(2) bond length. There is one shorter (3.41 Å) and one longer (3.58 Å) Rb(1)-S(4) bond length. There are a spread of Rb(1)-S(1) bond distances ranging from 3.36-3.47 Å. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. The Rb(2)-S(4) bond length is 3.52 Å. There is one shorter (3.48 Å) and one longer (3.57 Å) Rb(2)-S(1) bond length. There is one shorter (3.47 Å) and one longer (3.54 Å) Rb(2)-S(2) bond length. There are a spread of Rb(2)-S(3) bond distances ranging from 3.38-3.76 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Rb(2), three equivalent Rb(1), and one S(2) atom. The S(1)-S(2) bond length is 2.05 Å. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one S(1), and one S(5) atom. The S(2)-S(5) bond length is 2.08 Å. In the third S site, S(3) is bonded to one Rb(1), four equivalent Rb(2), and one S(4) atom to form a mixture of distorted edge and corner-sharing SRb5S pentagonal pyramids. The S(3)-S(4) bond length is 2.04 Å. In the fourth S site, S(4) is bonded in a distorted pentagonal planar geometry to one Rb(2), two equivalent Rb(1), one S(3), and one S(5) atom. The S(4)-S(5) bond length is 2.07 Å. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one S(2), and one S(4) atom.