Rb4In2S5 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(4), and three equivalent S(5) atoms. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to one S(2), one S(5), two equivalent S(1), and two equivalent S(3) atoms. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(3), one S(5), and two equivalent S(2) atoms to form a mixture of edge and corner-sharing InS4 tetrahedra. In the second In site, In(2) is bonded to one S(1), one S(3), and two equivalent S(4) atoms to form a mixture of edge and corner-sharing InS4 tetrahedra. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(4), two equivalent Rb(2), two equivalent Rb(3), and one In(2) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and two equivalent In(1) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Rb(2), two equivalent Rb(3), two equivalent Rb(4), one In(1), and one In(2) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(4), and two equivalent In(2) atoms. In the fifth S site, S(5) is bonded in a 7-coordinate geometry to one Rb(3), two equivalent Rb(4), three equivalent Rb(1), and one In(1) atom.
Rb4In2S5 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(4), and three equivalent S(5) atoms. The Rb(1)-S(1) bond length is 3.34 Å. The Rb(1)-S(2) bond length is 3.43 Å. The Rb(1)-S(4) bond length is 3.36 Å. There are a spread of Rb(1)-S(5) bond distances ranging from 3.44-3.87 Å. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. The Rb(2)-S(3) bond length is 3.19 Å. The Rb(2)-S(4) bond length is 3.76 Å. There is one shorter (3.27 Å) and one longer (3.33 Å) Rb(2)-S(1) bond length. There is one shorter (3.24 Å) and one longer (3.48 Å) Rb(2)-S(2) bond length. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to one S(2), one S(5), two equivalent S(1), and two equivalent S(3) atoms. The Rb(3)-S(2) bond length is 3.74 Å. The Rb(3)-S(5) bond length is 3.29 Å. There is one shorter (3.47 Å) and one longer (3.83 Å) Rb(3)-S(1) bond length. There is one shorter (3.44 Å) and one longer (3.66 Å) Rb(3)-S(3) bond length. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. The Rb(4)-S(1) bond length is 3.64 Å. There is one shorter (3.51 Å) and one longer (3.87 Å) Rb(4)-S(3) bond length. There is one shorter (3.48 Å) and one longer (3.76 Å) Rb(4)-S(4) bond length. There is one shorter (3.35 Å) and one longer (3.56 Å) Rb(4)-S(5) bond length. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(3), one S(5), and two equivalent S(2) atoms to form a mixture of edge and corner-sharing InS4 tetrahedra. The In(1)-S(3) bond length is 2.52 Å. The In(1)-S(5) bond length is 2.39 Å. There is one shorter (2.51 Å) and one longer (2.54 Å) In(1)-S(2) bond length. In the second In site, In(2) is bonded to one S(1), one S(3), and two equivalent S(4) atoms to form a mixture of edge and corner-sharing InS4 tetrahedra. The In(2)-S(1) bond length is 2.40 Å. The In(2)-S(3) bond length is 2.49 Å. There is one shorter (2.50 Å) and one longer (2.51 Å) In(2)-S(4) bond length. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(4), two equivalent Rb(2), two equivalent Rb(3), and one In(2) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and two equivalent In(1) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Rb(2), two equivalent Rb(3), two equivalent Rb(4), one In(1), and one In(2) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(4), and two equivalent In(2) atoms. In the fifth S site, S(5) is bonded in a 7-coordinate geometry to one Rb(3), two equivalent Rb(4), three equivalent Rb(1), and one In(1) atom.