Pr5N3S2Cl2 crystallizes in the monoclinic C2/m space group. There are five inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 1-coordinate geometry to one N(2), one S(1), one S(2), two equivalent Cl(1), and two equivalent Cl(2) atoms. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one N(2), two equivalent N(1), two equivalent S(1), one Cl(2), and two equivalent Cl(1) atoms. In the third Pr site, Pr(3) is bonded in a 6-coordinate geometry to two equivalent N(3), two equivalent S(1), and two equivalent S(2) atoms. In the fourth Pr site, Pr(4) is bonded in a 7-coordinate geometry to two equivalent N(3), one S(1), three equivalent S(2), and one Cl(1) atom. In the fifth Pr site, Pr(5) is bonded to two equivalent N(1), two equivalent N(2), and three equivalent Cl(2) atoms to form distorted edge-sharing PrN4Cl3 trigonal pyramids. There are three inequivalent N sites. In the first N site, N(3) is bonded to two equivalent Pr(3) and two equivalent Pr(4) atoms to form NPr4 tetrahedra that share corners with two equivalent S(1)Pr6 octahedra, corners with four equivalent S(2)Pr6 octahedra, corners with two equivalent N(3)Pr4 tetrahedra, edges with two equivalent S(1)Pr6 octahedra, edges with three equivalent S(2)Pr6 octahedra, and  an edgeedge with one N(3)Pr4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-47°. In the second N site, N(1) is bonded to two equivalent Pr(2) and two equivalent Pr(5) atoms to form NPr4 trigonal pyramids that share corners with two equivalent S(1)Pr6 octahedra, corners with four equivalent Cl(2)Pr6 octahedra, corners with two equivalent N(2)Pr4 tetrahedra, corners with two equivalent N(1)Pr4 trigonal pyramids,  an edgeedge with one S(1)Pr6 octahedra, edges with two equivalent Cl(2)Pr6 octahedra, edges with two equivalent N(2)Pr4 tetrahedra, and  an edgeedge with one N(1)Pr4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 32-47°. In the third N site, N(2) is bonded to one Pr(1), one Pr(2), and two equivalent Pr(5) atoms to form NPr4 tetrahedra that share  a cornercorner with one S(2)Pr6 octahedra, corners with three equivalent S(1)Pr6 octahedra, corners with three equivalent Cl(2)Pr6 octahedra, corners with two equivalent N(2)Pr4 tetrahedra, corners with two equivalent N(1)Pr4 trigonal pyramids, edges with three equivalent Cl(2)Pr6 octahedra, and edges with two equivalent N(1)Pr4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 19-50°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Pr(1), one Pr(4), two equivalent Pr(2), and two equivalent Pr(3) atoms to form distorted SPr6 octahedra that share corners with five equivalent S(2)Pr6 octahedra, corners with two equivalent N(3)Pr4 tetrahedra, corners with three equivalent N(2)Pr4 tetrahedra, corners with two equivalent N(1)Pr4 trigonal pyramids, edges with two equivalent S(1)Pr6 octahedra, edges with two equivalent Cl(2)Pr6 octahedra, edges with two equivalent N(3)Pr4 tetrahedra,  an edgeedge with one N(1)Pr4 trigonal pyramid, and  a faceface with one S(2)Pr6 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. In the second S site, S(2) is bonded to one Pr(1), two equivalent Pr(3), and three equivalent Pr(4) atoms to form distorted SPr6 octahedra that share corners with two equivalent Cl(2)Pr6 octahedra, corners with five equivalent S(1)Pr6 octahedra,  a cornercorner with one N(2)Pr4 tetrahedra, corners with four equivalent N(3)Pr4 tetrahedra, edges with four equivalent S(2)Pr6 octahedra, edges with three equivalent N(3)Pr4 tetrahedra, and  a faceface with one S(1)Pr6 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Pr(4), two equivalent Pr(1), and two equivalent Pr(2) atoms. In the second Cl site, Cl(2) is bonded to one Pr(2), two equivalent Pr(1), and three equivalent Pr(5) atoms to form distorted ClPr6 octahedra that share corners with two equivalent S(2)Pr6 octahedra, corners with three equivalent N(2)Pr4 tetrahedra, corners with four equivalent N(1)Pr4 trigonal pyramids, edges with two equivalent S(1)Pr6 octahedra, edges with four equivalent Cl(2)Pr6 octahedra, edges with three equivalent N(2)Pr4 tetrahedra, and edges with two equivalent N(1)Pr4 trigonal pyramids. The corner-sharing octahedral tilt angles are 52°.
Pr5N3S2Cl2 crystallizes in the monoclinic C2/m space group. There are five inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 1-coordinate geometry to one N(2), one S(1), one S(2), two equivalent Cl(1), and two equivalent Cl(2) atoms. The Pr(1)-N(2) bond length is 2.20 Å. The Pr(1)-S(1) bond length is 3.13 Å. The Pr(1)-S(2) bond length is 3.35 Å. Both Pr(1)-Cl(1) bond lengths are 2.85 Å. Both Pr(1)-Cl(2) bond lengths are 2.92 Å. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one N(2), two equivalent N(1), two equivalent S(1), one Cl(2), and two equivalent Cl(1) atoms. The Pr(2)-N(2) bond length is 2.45 Å. Both Pr(2)-N(1) bond lengths are 2.39 Å. Both Pr(2)-S(1) bond lengths are 3.26 Å. The Pr(2)-Cl(2) bond length is 3.11 Å. Both Pr(2)-Cl(1) bond lengths are 3.29 Å. In the third Pr site, Pr(3) is bonded in a 6-coordinate geometry to two equivalent N(3), two equivalent S(1), and two equivalent S(2) atoms. There is one shorter (2.35 Å) and one longer (2.40 Å) Pr(3)-N(3) bond length. Both Pr(3)-S(1) bond lengths are 2.95 Å. Both Pr(3)-S(2) bond lengths are 3.00 Å. In the fourth Pr site, Pr(4) is bonded in a 7-coordinate geometry to two equivalent N(3), one S(1), three equivalent S(2), and one Cl(1) atom. Both Pr(4)-N(3) bond lengths are 2.40 Å. The Pr(4)-S(1) bond length is 3.33 Å. There is one shorter (2.89 Å) and two longer (3.17 Å) Pr(4)-S(2) bond lengths. The Pr(4)-Cl(1) bond length is 2.93 Å. In the fifth Pr site, Pr(5) is bonded to two equivalent N(1), two equivalent N(2), and three equivalent Cl(2) atoms to form distorted edge-sharing PrN4Cl3 trigonal pyramids. There is one shorter (2.33 Å) and one longer (2.40 Å) Pr(5)-N(1) bond length. Both Pr(5)-N(2) bond lengths are 2.44 Å. There is one shorter (3.26 Å) and two longer (3.43 Å) Pr(5)-Cl(2) bond lengths. There are three inequivalent N sites. In the first N site, N(3) is bonded to two equivalent Pr(3) and two equivalent Pr(4) atoms to form NPr4 tetrahedra that share corners with two equivalent S(1)Pr6 octahedra, corners with four equivalent S(2)Pr6 octahedra, corners with two equivalent N(3)Pr4 tetrahedra, edges with two equivalent S(1)Pr6 octahedra, edges with three equivalent S(2)Pr6 octahedra, and  an edgeedge with one N(3)Pr4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-47°. In the second N site, N(1) is bonded to two equivalent Pr(2) and two equivalent Pr(5) atoms to form NPr4 trigonal pyramids that share corners with two equivalent S(1)Pr6 octahedra, corners with four equivalent Cl(2)Pr6 octahedra, corners with two equivalent N(2)Pr4 tetrahedra, corners with two equivalent N(1)Pr4 trigonal pyramids,  an edgeedge with one S(1)Pr6 octahedra, edges with two equivalent Cl(2)Pr6 octahedra, edges with two equivalent N(2)Pr4 tetrahedra, and  an edgeedge with one N(1)Pr4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 32-47°. In the third N site, N(2) is bonded to one Pr(1), one Pr(2), and two equivalent Pr(5) atoms to form NPr4 tetrahedra that share  a cornercorner with one S(2)Pr6 octahedra, corners with three equivalent S(1)Pr6 octahedra, corners with three equivalent Cl(2)Pr6 octahedra, corners with two equivalent N(2)Pr4 tetrahedra, corners with two equivalent N(1)Pr4 trigonal pyramids, edges with three equivalent Cl(2)Pr6 octahedra, and edges with two equivalent N(1)Pr4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 19-50°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Pr(1), one Pr(4), two equivalent Pr(2), and two equivalent Pr(3) atoms to form distorted SPr6 octahedra that share corners with five equivalent S(2)Pr6 octahedra, corners with two equivalent N(3)Pr4 tetrahedra, corners with three equivalent N(2)Pr4 tetrahedra, corners with two equivalent N(1)Pr4 trigonal pyramids, edges with two equivalent S(1)Pr6 octahedra, edges with two equivalent Cl(2)Pr6 octahedra, edges with two equivalent N(3)Pr4 tetrahedra,  an edgeedge with one N(1)Pr4 trigonal pyramid, and  a faceface with one S(2)Pr6 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. In the second S site, S(2) is bonded to one Pr(1), two equivalent Pr(3), and three equivalent Pr(4) atoms to form distorted SPr6 octahedra that share corners with two equivalent Cl(2)Pr6 octahedra, corners with five equivalent S(1)Pr6 octahedra,  a cornercorner with one N(2)Pr4 tetrahedra, corners with four equivalent N(3)Pr4 tetrahedra, edges with four equivalent S(2)Pr6 octahedra, edges with three equivalent N(3)Pr4 tetrahedra, and  a faceface with one S(1)Pr6 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Pr(4), two equivalent Pr(1), and two equivalent Pr(2) atoms. In the second Cl site, Cl(2) is bonded to one Pr(2), two equivalent Pr(1), and three equivalent Pr(5) atoms to form distorted ClPr6 octahedra that share corners with two equivalent S(2)Pr6 octahedra, corners with three equivalent N(2)Pr4 tetrahedra, corners with four equivalent N(1)Pr4 trigonal pyramids, edges with two equivalent S(1)Pr6 octahedra, edges with four equivalent Cl(2)Pr6 octahedra, edges with three equivalent N(2)Pr4 tetrahedra, and edges with two equivalent N(1)Pr4 trigonal pyramids. The corner-sharing octahedral tilt angles are 52°.