Pr5S9 crystallizes in the monoclinic C2 space group. There are five inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one S(10), one S(2), one S(6), one S(7), two equivalent S(1), and two equivalent S(3) atoms. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to one S(2), one S(3), one S(4), two equivalent S(5), two equivalent S(8), and two equivalent S(9) atoms. In the third Pr site, Pr(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(4), one S(5), one S(6), one S(7), and two equivalent S(2) atoms. In the fourth Pr site, Pr(4) is bonded in a 8-coordinate geometry to one S(5), one S(7), one S(8), one S(9), two equivalent S(1), and two equivalent S(3) atoms. In the fifth Pr site, Pr(5) is bonded in a 8-coordinate geometry to one S(2), one S(5), one S(7), one S(8), one S(9), and three equivalent S(4) atoms. There are ten inequivalent S sites. In the first S site, S(8) is bonded in a 4-coordinate geometry to one Pr(4), one Pr(5), and two equivalent Pr(2) atoms. In the second S site, S(9) is bonded in a 4-coordinate geometry to one Pr(4), one Pr(5), and two equivalent Pr(2) atoms. In the third S site, S(10) is bonded in a 8-coordinate geometry to two equivalent Pr(1), two equivalent Pr(3), two equivalent S(6), and two equivalent S(7) atoms. In the fourth S site, S(1) is bonded to one Pr(3), two equivalent Pr(1), and two equivalent Pr(4) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the fifth S site, S(2) is bonded to one Pr(1), one Pr(2), one Pr(5), and two equivalent Pr(3) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the sixth S site, S(3) is bonded to one Pr(2), two equivalent Pr(1), and two equivalent Pr(4) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the seventh S site, S(4) is bonded to one Pr(2), one Pr(3), and three equivalent Pr(5) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the eighth S site, S(5) is bonded to one Pr(3), one Pr(4), one Pr(5), and two equivalent Pr(2) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the ninth S site, S(6) is bonded in a 4-coordinate geometry to two equivalent Pr(1), two equivalent Pr(3), and two equivalent S(10) atoms. In the tenth S site, S(7) is bonded in a 5-coordinate geometry to one Pr(1), one Pr(3), one Pr(4), one Pr(5), and one S(10) atom.
Pr5S9 crystallizes in the monoclinic C2 space group. There are five inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one S(10), one S(2), one S(6), one S(7), two equivalent S(1), and two equivalent S(3) atoms. The Pr(1)-S(10) bond length is 3.02 Å. The Pr(1)-S(2) bond length is 2.95 Å. The Pr(1)-S(6) bond length is 3.02 Å. The Pr(1)-S(7) bond length is 2.91 Å. There is one shorter (2.88 Å) and one longer (2.89 Å) Pr(1)-S(1) bond length. Both Pr(1)-S(3) bond lengths are 2.95 Å. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to one S(2), one S(3), one S(4), two equivalent S(5), two equivalent S(8), and two equivalent S(9) atoms. The Pr(2)-S(2) bond length is 3.03 Å. The Pr(2)-S(3) bond length is 3.07 Å. The Pr(2)-S(4) bond length is 3.09 Å. There is one shorter (2.91 Å) and one longer (2.92 Å) Pr(2)-S(5) bond length. Both Pr(2)-S(8) bond lengths are 3.06 Å. There is one shorter (2.96 Å) and one longer (2.97 Å) Pr(2)-S(9) bond length. In the third Pr site, Pr(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(4), one S(5), one S(6), one S(7), and two equivalent S(2) atoms. The Pr(3)-S(1) bond length is 2.93 Å. The Pr(3)-S(10) bond length is 3.04 Å. The Pr(3)-S(4) bond length is 2.93 Å. The Pr(3)-S(5) bond length is 2.95 Å. The Pr(3)-S(6) bond length is 3.04 Å. The Pr(3)-S(7) bond length is 2.91 Å. There is one shorter (2.88 Å) and one longer (2.90 Å) Pr(3)-S(2) bond length. In the fourth Pr site, Pr(4) is bonded in a 8-coordinate geometry to one S(5), one S(7), one S(8), one S(9), two equivalent S(1), and two equivalent S(3) atoms. The Pr(4)-S(5) bond length is 3.00 Å. The Pr(4)-S(7) bond length is 3.14 Å. The Pr(4)-S(8) bond length is 2.90 Å. The Pr(4)-S(9) bond length is 2.91 Å. There is one shorter (2.95 Å) and one longer (2.96 Å) Pr(4)-S(1) bond length. There is one shorter (2.86 Å) and one longer (2.90 Å) Pr(4)-S(3) bond length. In the fifth Pr site, Pr(5) is bonded in a 8-coordinate geometry to one S(2), one S(5), one S(7), one S(8), one S(9), and three equivalent S(4) atoms. The Pr(5)-S(2) bond length is 2.96 Å. The Pr(5)-S(5) bond length is 3.02 Å. The Pr(5)-S(7) bond length is 3.14 Å. The Pr(5)-S(8) bond length is 2.91 Å. The Pr(5)-S(9) bond length is 2.91 Å. There are a spread of Pr(5)-S(4) bond distances ranging from 2.87-2.96 Å. There are ten inequivalent S sites. In the first S site, S(8) is bonded in a 4-coordinate geometry to one Pr(4), one Pr(5), and two equivalent Pr(2) atoms. In the second S site, S(9) is bonded in a 4-coordinate geometry to one Pr(4), one Pr(5), and two equivalent Pr(2) atoms. In the third S site, S(10) is bonded in a 8-coordinate geometry to two equivalent Pr(1), two equivalent Pr(3), two equivalent S(6), and two equivalent S(7) atoms. There is one shorter (2.78 Å) and one longer (2.79 Å) S(10)-S(6) bond length. Both S(10)-S(7) bond lengths are 2.51 Å. In the fourth S site, S(1) is bonded to one Pr(3), two equivalent Pr(1), and two equivalent Pr(4) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the fifth S site, S(2) is bonded to one Pr(1), one Pr(2), one Pr(5), and two equivalent Pr(3) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the sixth S site, S(3) is bonded to one Pr(2), two equivalent Pr(1), and two equivalent Pr(4) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the seventh S site, S(4) is bonded to one Pr(2), one Pr(3), and three equivalent Pr(5) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the eighth S site, S(5) is bonded to one Pr(3), one Pr(4), one Pr(5), and two equivalent Pr(2) atoms to form a mixture of distorted edge and corner-sharing SPr5 trigonal bipyramids. In the ninth S site, S(6) is bonded in a 4-coordinate geometry to two equivalent Pr(1), two equivalent Pr(3), and two equivalent S(10) atoms. In the tenth S site, S(7) is bonded in a 5-coordinate geometry to one Pr(1), one Pr(3), one Pr(4), one Pr(5), and one S(10) atom.