Pr6Mn(SiS7)2 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(1), one S(6), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one S(2), one S(5), two equivalent S(3), two equivalent S(4), and two equivalent S(6) atoms. Mn(1) is bonded in an octahedral geometry to three equivalent S(3) and three equivalent S(4) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a tetrahedral geometry to one S(1) and three equivalent S(5) atoms. In the second Si site, Si(2) is bonded in a tetrahedral geometry to one S(2) and three equivalent S(6) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Pr(1) and one Si(1) atom to form distorted corner-sharing SPr3Si tetrahedra. In the second S site, S(2) is bonded to three equivalent Pr(2) and one Si(2) atom to form distorted corner-sharing SPr3Si tetrahedra. In the third S site, S(3) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Mn(1) atom to form distorted SPr4Mn trigonal bipyramids that share corners with two equivalent S(1)Pr3Si tetrahedra, corners with two equivalent S(2)Pr3Si tetrahedra,  a cornercorner with one S(4)Pr4Mn trigonal bipyramid, corners with two equivalent S(3)Pr4Mn trigonal bipyramids, edges with two equivalent S(3)Pr4Mn trigonal bipyramids, edges with two equivalent S(4)Pr4Mn trigonal bipyramids, and faces with two equivalent S(4)Pr4Mn trigonal bipyramids. In the fourth S site, S(4) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Mn(1) atom to form distorted SPr4Mn trigonal bipyramids that share corners with two equivalent S(1)Pr3Si tetrahedra, corners with two equivalent S(2)Pr3Si tetrahedra,  a cornercorner with one S(3)Pr4Mn trigonal bipyramid, corners with two equivalent S(4)Pr4Mn trigonal bipyramids, edges with two equivalent S(3)Pr4Mn trigonal bipyramids, edges with two equivalent S(4)Pr4Mn trigonal bipyramids, and faces with two equivalent S(3)Pr4Mn trigonal bipyramids. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to one Pr(2), two equivalent Pr(1), and one Si(1) atom. In the sixth S site, S(6) is bonded in a distorted rectangular see-saw-like geometry to one Pr(1), two equivalent Pr(2), and one Si(2) atom.
Pr6Mn(SiS7)2 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(1), one S(6), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. The Pr(1)-S(1) bond length is 3.08 Å. The Pr(1)-S(6) bond length is 3.05 Å. There is one shorter (2.93 Å) and one longer (3.16 Å) Pr(1)-S(3) bond length. There is one shorter (2.84 Å) and one longer (2.88 Å) Pr(1)-S(4) bond length. There is one shorter (2.91 Å) and one longer (3.00 Å) Pr(1)-S(5) bond length. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one S(2), one S(5), two equivalent S(3), two equivalent S(4), and two equivalent S(6) atoms. The Pr(2)-S(2) bond length is 3.09 Å. The Pr(2)-S(5) bond length is 3.03 Å. Both Pr(2)-S(3) bond lengths are 2.86 Å. There is one shorter (3.03 Å) and one longer (3.06 Å) Pr(2)-S(4) bond length. There is one shorter (2.91 Å) and one longer (3.00 Å) Pr(2)-S(6) bond length. Mn(1) is bonded in an octahedral geometry to three equivalent S(3) and three equivalent S(4) atoms. All Mn(1)-S(3) bond lengths are 2.60 Å. All Mn(1)-S(4) bond lengths are 2.60 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a tetrahedral geometry to one S(1) and three equivalent S(5) atoms. The Si(1)-S(1) bond length is 2.10 Å. All Si(1)-S(5) bond lengths are 2.15 Å. In the second Si site, Si(2) is bonded in a tetrahedral geometry to one S(2) and three equivalent S(6) atoms. The Si(2)-S(2) bond length is 2.10 Å. All Si(2)-S(6) bond lengths are 2.15 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Pr(1) and one Si(1) atom to form distorted corner-sharing SPr3Si tetrahedra. In the second S site, S(2) is bonded to three equivalent Pr(2) and one Si(2) atom to form distorted corner-sharing SPr3Si tetrahedra. In the third S site, S(3) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Mn(1) atom to form distorted SPr4Mn trigonal bipyramids that share corners with two equivalent S(1)Pr3Si tetrahedra, corners with two equivalent S(2)Pr3Si tetrahedra,  a cornercorner with one S(4)Pr4Mn trigonal bipyramid, corners with two equivalent S(3)Pr4Mn trigonal bipyramids, edges with two equivalent S(3)Pr4Mn trigonal bipyramids, edges with two equivalent S(4)Pr4Mn trigonal bipyramids, and faces with two equivalent S(4)Pr4Mn trigonal bipyramids. In the fourth S site, S(4) is bonded to two equivalent Pr(1), two equivalent Pr(2), and one Mn(1) atom to form distorted SPr4Mn trigonal bipyramids that share corners with two equivalent S(1)Pr3Si tetrahedra, corners with two equivalent S(2)Pr3Si tetrahedra,  a cornercorner with one S(3)Pr4Mn trigonal bipyramid, corners with two equivalent S(4)Pr4Mn trigonal bipyramids, edges with two equivalent S(3)Pr4Mn trigonal bipyramids, edges with two equivalent S(4)Pr4Mn trigonal bipyramids, and faces with two equivalent S(3)Pr4Mn trigonal bipyramids. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to one Pr(2), two equivalent Pr(1), and one Si(1) atom. In the sixth S site, S(6) is bonded in a distorted rectangular see-saw-like geometry to one Pr(1), two equivalent Pr(2), and one Si(2) atom.