Pr6Ge3S14 crystallizes in the trigonal P3 space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one S(2), one S(3), two equivalent S(1), two equivalent S(5), and two equivalent S(6) atoms. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a tetrahedral geometry to one S(3) and three equivalent S(1) atoms. In the second Ge site, Ge(2) is bonded in a tetrahedral geometry to one S(4) and three equivalent S(2) atoms. In the third Ge site, Ge(3) is bonded in an octahedral geometry to three equivalent S(5) and three equivalent S(6) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Pr(2), two equivalent Pr(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Pr(1), two equivalent Pr(2), and one Ge(2) atom. In the third S site, S(3) is bonded to three equivalent Pr(1) and one Ge(1) atom to form corner-sharing SPr3Ge tetrahedra. In the fourth S site, S(4) is bonded to three equivalent Pr(2) and one Ge(2) atom to form corner-sharing SPr3Ge tetrahedra. In the fifth S site, S(5) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Ge(3) atom to form distorted SPr4Ge trigonal bipyramids that share corners with two equivalent S(3)Pr3Ge tetrahedra, corners with two equivalent S(4)Pr3Ge tetrahedra,  a cornercorner with one S(6)Pr4Ge trigonal bipyramid, corners with two equivalent S(5)Pr4Ge trigonal bipyramids, edges with two equivalent S(5)Pr4Ge trigonal bipyramids, edges with two equivalent S(6)Pr4Ge trigonal bipyramids, and faces with two equivalent S(6)Pr4Ge trigonal bipyramids. In the sixth S site, S(6) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Ge(3) atom to form distorted SPr4Ge trigonal bipyramids that share corners with two equivalent S(3)Pr3Ge tetrahedra, corners with two equivalent S(4)Pr3Ge tetrahedra,  a cornercorner with one S(5)Pr4Ge trigonal bipyramid, corners with two equivalent S(6)Pr4Ge trigonal bipyramids, edges with two equivalent S(5)Pr4Ge trigonal bipyramids, edges with two equivalent S(6)Pr4Ge trigonal bipyramids, and faces with two equivalent S(5)Pr4Ge trigonal bipyramids.
Pr6Ge3S14 crystallizes in the trigonal P3 space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one S(2), one S(3), two equivalent S(1), two equivalent S(5), and two equivalent S(6) atoms. The Pr(1)-S(2) bond length is 3.07 Å. The Pr(1)-S(3) bond length is 3.07 Å. There is one shorter (2.91 Å) and one longer (2.99 Å) Pr(1)-S(1) bond length. There is one shorter (2.96 Å) and one longer (3.16 Å) Pr(1)-S(5) bond length. There is one shorter (2.89 Å) and one longer (2.91 Å) Pr(1)-S(6) bond length. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. The Pr(2)-S(1) bond length is 3.04 Å. The Pr(2)-S(4) bond length is 3.06 Å. There is one shorter (2.91 Å) and one longer (2.99 Å) Pr(2)-S(2) bond length. There is one shorter (2.89 Å) and one longer (2.91 Å) Pr(2)-S(5) bond length. There is one shorter (2.98 Å) and one longer (3.13 Å) Pr(2)-S(6) bond length. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a tetrahedral geometry to one S(3) and three equivalent S(1) atoms. The Ge(1)-S(3) bond length is 2.18 Å. All Ge(1)-S(1) bond lengths are 2.23 Å. In the second Ge site, Ge(2) is bonded in a tetrahedral geometry to one S(4) and three equivalent S(2) atoms. The Ge(2)-S(4) bond length is 2.18 Å. All Ge(2)-S(2) bond lengths are 2.23 Å. In the third Ge site, Ge(3) is bonded in an octahedral geometry to three equivalent S(5) and three equivalent S(6) atoms. All Ge(3)-S(5) bond lengths are 2.68 Å. All Ge(3)-S(6) bond lengths are 2.74 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Pr(2), two equivalent Pr(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Pr(1), two equivalent Pr(2), and one Ge(2) atom. In the third S site, S(3) is bonded to three equivalent Pr(1) and one Ge(1) atom to form corner-sharing SPr3Ge tetrahedra. In the fourth S site, S(4) is bonded to three equivalent Pr(2) and one Ge(2) atom to form corner-sharing SPr3Ge tetrahedra. In the fifth S site, S(5) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Ge(3) atom to form distorted SPr4Ge trigonal bipyramids that share corners with two equivalent S(3)Pr3Ge tetrahedra, corners with two equivalent S(4)Pr3Ge tetrahedra,  a cornercorner with one S(6)Pr4Ge trigonal bipyramid, corners with two equivalent S(5)Pr4Ge trigonal bipyramids, edges with two equivalent S(5)Pr4Ge trigonal bipyramids, edges with two equivalent S(6)Pr4Ge trigonal bipyramids, and faces with two equivalent S(6)Pr4Ge trigonal bipyramids. In the sixth S site, S(6) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Ge(3) atom to form distorted SPr4Ge trigonal bipyramids that share corners with two equivalent S(3)Pr3Ge tetrahedra, corners with two equivalent S(4)Pr3Ge tetrahedra,  a cornercorner with one S(5)Pr4Ge trigonal bipyramid, corners with two equivalent S(6)Pr4Ge trigonal bipyramids, edges with two equivalent S(5)Pr4Ge trigonal bipyramids, edges with two equivalent S(6)Pr4Ge trigonal bipyramids, and faces with two equivalent S(5)Pr4Ge trigonal bipyramids.