Pr3Si2S8Cl crystallizes in the monoclinic C2/c space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(4), three equivalent S(3), and one Cl(1) atom. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to two equivalent S(2), two equivalent S(4), four equivalent S(1), and one Cl(1) atom. Si(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Pr(1), two equivalent Pr(2), and one Si(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Pr(2), two equivalent Pr(1), and one Si(1) atom. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Pr(1) and one Si(1) atom. In the fourth S site, S(4) is bonded to one Pr(2), two equivalent Pr(1), and one Si(1) atom to form distorted corner-sharing SPr3Si trigonal pyramids. Cl(1) is bonded in a 3-coordinate geometry to one Pr(2) and two equivalent Pr(1) atoms.
Pr3Si2S8Cl crystallizes in the monoclinic C2/c space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(4), three equivalent S(3), and one Cl(1) atom. The Pr(1)-S(1) bond length is 2.93 Å. There is one shorter (3.01 Å) and one longer (3.10 Å) Pr(1)-S(2) bond length. There is one shorter (2.96 Å) and one longer (3.02 Å) Pr(1)-S(4) bond length. There are a spread of Pr(1)-S(3) bond distances ranging from 2.93-3.08 Å. The Pr(1)-Cl(1) bond length is 3.42 Å. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to two equivalent S(2), two equivalent S(4), four equivalent S(1), and one Cl(1) atom. Both Pr(2)-S(2) bond lengths are 2.91 Å. Both Pr(2)-S(4) bond lengths are 2.91 Å. There are two shorter (3.34 Å) and two longer (3.36 Å) Pr(2)-S(1) bond lengths. The Pr(2)-Cl(1) bond length is 2.87 Å. Si(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Si(1)-S(1) bond length is 2.12 Å. The Si(1)-S(2) bond length is 2.12 Å. The Si(1)-S(3) bond length is 2.14 Å. The Si(1)-S(4) bond length is 2.13 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Pr(1), two equivalent Pr(2), and one Si(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Pr(2), two equivalent Pr(1), and one Si(1) atom. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Pr(1) and one Si(1) atom. In the fourth S site, S(4) is bonded to one Pr(2), two equivalent Pr(1), and one Si(1) atom to form distorted corner-sharing SPr3Si trigonal pyramids. Cl(1) is bonded in a 3-coordinate geometry to one Pr(2) and two equivalent Pr(1) atoms.