Cs4In2S5 crystallizes in the triclinic P-1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), two equivalent S(3), and two equivalent S(5) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(2), one S(5), two equivalent S(1), and two equivalent S(4) atoms. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms. In the fourth Cs site, Cs(4) is bonded in a 6-coordinate geometry to one S(1), one S(3), one S(5), and three equivalent S(4) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(2), one S(5), and two equivalent S(1) atoms to form a mixture of corner and edge-sharing InS4 tetrahedra. In the second In site, In(2) is bonded to one S(2), one S(4), and two equivalent S(3) atoms to form a mixture of corner and edge-sharing InS4 tetrahedra. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(4), two equivalent Cs(2), and two equivalent In(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), two equivalent Cs(3), one In(1), and one In(2) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and two equivalent In(2) atoms. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Cs(3), two equivalent Cs(2), three equivalent Cs(4), and one In(2) atom. In the fifth S site, S(5) is bonded in a 7-coordinate geometry to one Cs(2), one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and one In(1) atom.
Cs4In2S5 crystallizes in the triclinic P-1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), two equivalent S(3), and two equivalent S(5) atoms. The Cs(1)-S(1) bond length is 3.86 Å. The Cs(1)-S(2) bond length is 3.39 Å. There is one shorter (3.42 Å) and one longer (3.62 Å) Cs(1)-S(3) bond length. There is one shorter (3.46 Å) and one longer (3.51 Å) Cs(1)-S(5) bond length. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(2), one S(5), two equivalent S(1), and two equivalent S(4) atoms. The Cs(2)-S(2) bond length is 3.59 Å. The Cs(2)-S(5) bond length is 3.73 Å. There is one shorter (3.67 Å) and one longer (3.81 Å) Cs(2)-S(1) bond length. There is one shorter (3.48 Å) and one longer (3.70 Å) Cs(2)-S(4) bond length. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms. The Cs(3)-S(4) bond length is 3.42 Å. There is one shorter (3.55 Å) and one longer (3.85 Å) Cs(3)-S(2) bond length. Both Cs(3)-S(3) bond lengths are 3.99 Å. There is one shorter (3.64 Å) and one longer (3.94 Å) Cs(3)-S(5) bond length. In the fourth Cs site, Cs(4) is bonded in a 6-coordinate geometry to one S(1), one S(3), one S(5), and three equivalent S(4) atoms. The Cs(4)-S(1) bond length is 3.60 Å. The Cs(4)-S(3) bond length is 3.58 Å. The Cs(4)-S(5) bond length is 3.53 Å. There are a spread of Cs(4)-S(4) bond distances ranging from 3.60-4.02 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(2), one S(5), and two equivalent S(1) atoms to form a mixture of corner and edge-sharing InS4 tetrahedra. The In(1)-S(2) bond length is 2.50 Å. The In(1)-S(5) bond length is 2.41 Å. There is one shorter (2.51 Å) and one longer (2.52 Å) In(1)-S(1) bond length. In the second In site, In(2) is bonded to one S(2), one S(4), and two equivalent S(3) atoms to form a mixture of corner and edge-sharing InS4 tetrahedra. The In(2)-S(2) bond length is 2.52 Å. The In(2)-S(4) bond length is 2.40 Å. There is one shorter (2.52 Å) and one longer (2.54 Å) In(2)-S(3) bond length. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(4), two equivalent Cs(2), and two equivalent In(1) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), two equivalent Cs(3), one In(1), and one In(2) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and two equivalent In(2) atoms. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Cs(3), two equivalent Cs(2), three equivalent Cs(4), and one In(2) atom. In the fifth S site, S(5) is bonded in a 7-coordinate geometry to one Cs(2), one Cs(4), two equivalent Cs(1), two equivalent Cs(3), and one In(1) atom.