Cs2Ge2S5 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(1), one S(5), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one S(6), two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(1), one S(3), one S(4), and one S(5) atom to form corner-sharing GeS4 tetrahedra. In the second Ge site, Ge(2) is bonded to one S(1), one S(2), one S(5), and one S(6) atom to form corner-sharing GeS4 tetrahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to one Cs(1), two equivalent Cs(2), one Ge(1), and one Ge(2) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Ge(2) atom. In the third S site, S(3) is bonded in a distorted water-like geometry to four equivalent Cs(1) and two equivalent Ge(1) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Cs(1), two equivalent Cs(2), one Ge(1), and one Ge(2) atom. In the sixth S site, S(6) is bonded in a distorted water-like geometry to two equivalent Cs(2) and two equivalent Ge(2) atoms.
Cs2Ge2S5 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(1), one S(5), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. The Cs(1)-S(1) bond length is 3.83 Å. The Cs(1)-S(5) bond length is 3.72 Å. There is one shorter (3.53 Å) and one longer (4.14 Å) Cs(1)-S(2) bond length. There is one shorter (3.83 Å) and one longer (4.08 Å) Cs(1)-S(3) bond length. There are a spread of Cs(1)-S(4) bond distances ranging from 3.48-3.94 Å. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one S(6), two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. The Cs(2)-S(6) bond length is 3.86 Å. There is one shorter (3.91 Å) and one longer (4.17 Å) Cs(2)-S(1) bond length. There is one shorter (3.51 Å) and one longer (3.63 Å) Cs(2)-S(2) bond length. There is one shorter (3.56 Å) and one longer (4.01 Å) Cs(2)-S(4) bond length. There is one shorter (3.55 Å) and one longer (3.73 Å) Cs(2)-S(5) bond length. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(1), one S(3), one S(4), and one S(5) atom to form corner-sharing GeS4 tetrahedra. The Ge(1)-S(1) bond length is 2.23 Å. The Ge(1)-S(3) bond length is 2.26 Å. The Ge(1)-S(4) bond length is 2.13 Å. The Ge(1)-S(5) bond length is 2.25 Å. In the second Ge site, Ge(2) is bonded to one S(1), one S(2), one S(5), and one S(6) atom to form corner-sharing GeS4 tetrahedra. The Ge(2)-S(1) bond length is 2.27 Å. The Ge(2)-S(2) bond length is 2.12 Å. The Ge(2)-S(5) bond length is 2.26 Å. The Ge(2)-S(6) bond length is 2.25 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to one Cs(1), two equivalent Cs(2), one Ge(1), and one Ge(2) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Ge(2) atom. In the third S site, S(3) is bonded in a distorted water-like geometry to four equivalent Cs(1) and two equivalent Ge(1) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Cs(1), two equivalent Cs(2), one Ge(1), and one Ge(2) atom. In the sixth S site, S(6) is bonded in a distorted water-like geometry to two equivalent Cs(2) and two equivalent Ge(2) atoms.