Pr4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to three equivalent S(3) and six equivalent S(2) atoms. In the second Pr site, Pr(2) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms. Ge(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 3-coordinate geometry to two equivalent Pr(2) and one Ge(1) atom. In the second S site, S(2) is bonded to one Pr(2), two equivalent Pr(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SPr3Ge tetrahedra. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Pr(1), two equivalent Pr(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Pr(2) and one Ge(1) atom.
Pr4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to three equivalent S(3) and six equivalent S(2) atoms. All Pr(1)-S(3) bond lengths are 3.41 Å. All Pr(1)-S(2) bond lengths are 2.91 Å. In the second Pr site, Pr(2) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms. The Pr(2)-S(2) bond length is 2.92 Å. There is one shorter (2.90 Å) and one longer (2.99 Å) Pr(2)-S(1) bond length. There is one shorter (3.01 Å) and one longer (3.08 Å) Pr(2)-S(3) bond length. There is one shorter (2.88 Å) and one longer (2.96 Å) Pr(2)-S(4) bond length. Ge(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Ge(1)-S(1) bond length is 2.20 Å. The Ge(1)-S(2) bond length is 2.25 Å. The Ge(1)-S(3) bond length is 2.20 Å. The Ge(1)-S(4) bond length is 2.21 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Pr(2) and one Ge(1) atom. In the second S site, S(2) is bonded to one Pr(2), two equivalent Pr(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SPr3Ge tetrahedra. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Pr(1), two equivalent Pr(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Pr(2) and one Ge(1) atom.