Cs2S5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(2), two equivalent S(3), two equivalent S(5), and four equivalent S(1) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), two equivalent S(5), and three equivalent S(2) atoms. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to two equivalent Cs(2), four equivalent Cs(1), and one S(3) atom. In the second S site, S(2) is bonded to two equivalent Cs(1), three equivalent Cs(2), and one S(5) atom to form a mixture of distorted edge and corner-sharing SCs5S octahedra. The corner-sharing octahedral tilt angles range from 10-48°. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one S(1), and one S(4) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Cs(2), one S(3), and one S(5) atom. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one S(2), and one S(4) atom.
Cs2S5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(2), two equivalent S(3), two equivalent S(5), and four equivalent S(1) atoms. There is one shorter (3.53 Å) and one longer (3.76 Å) Cs(1)-S(2) bond length. There is one shorter (3.63 Å) and one longer (4.02 Å) Cs(1)-S(3) bond length. There is one shorter (3.58 Å) and one longer (3.65 Å) Cs(1)-S(5) bond length. There are a spread of Cs(1)-S(1) bond distances ranging from 3.56-3.86 Å. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), two equivalent S(5), and three equivalent S(2) atoms. The Cs(2)-S(4) bond length is 3.84 Å. There is one shorter (3.67 Å) and one longer (3.91 Å) Cs(2)-S(1) bond length. There is one shorter (3.64 Å) and one longer (3.72 Å) Cs(2)-S(3) bond length. There is one shorter (3.72 Å) and one longer (3.88 Å) Cs(2)-S(5) bond length. There are a spread of Cs(2)-S(2) bond distances ranging from 3.47-3.70 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to two equivalent Cs(2), four equivalent Cs(1), and one S(3) atom. The S(1)-S(3) bond length is 2.04 Å. In the second S site, S(2) is bonded to two equivalent Cs(1), three equivalent Cs(2), and one S(5) atom to form a mixture of distorted edge and corner-sharing SCs5S octahedra. The corner-sharing octahedral tilt angles range from 10-48°. The S(2)-S(5) bond length is 2.04 Å. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one S(1), and one S(4) atom. The S(3)-S(4) bond length is 2.08 Å. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one Cs(2), one S(3), and one S(5) atom. The S(4)-S(5) bond length is 2.08 Å. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one S(2), and one S(4) atom.