Pr2ZrS5 crystallizes in the orthorhombic Pnma space group. Pr(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. Zr(1) is bonded to one S(2), one S(3), one S(4), and four equivalent S(1) atoms to form distorted edge-sharing ZrS7 pentagonal bipyramids. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Pr(1) and two equivalent Zr(1) atoms to form distorted SPr2Zr2 trigonal pyramids that share corners with four equivalent S(3)Pr4Zr square pyramids, corners with two equivalent S(2)Pr4Zr trigonal bipyramids, corners with two equivalent S(4)Pr4Zr trigonal bipyramids, corners with six equivalent S(1)Pr2Zr2 trigonal pyramids,  an edgeedge with one S(3)Pr4Zr square pyramid, edges with two equivalent S(2)Pr4Zr trigonal bipyramids, edges with two equivalent S(4)Pr4Zr trigonal bipyramids, and  an edgeedge with one S(1)Pr2Zr2 trigonal pyramid. In the second S site, S(2) is bonded to four equivalent Pr(1) and one Zr(1) atom to form distorted SPr4Zr trigonal bipyramids that share corners with five equivalent S(3)Pr4Zr square pyramids,  a cornercorner with one S(4)Pr4Zr trigonal bipyramid, corners with four equivalent S(2)Pr4Zr trigonal bipyramids, corners with four equivalent S(1)Pr2Zr2 trigonal pyramids, edges with two equivalent S(3)Pr4Zr square pyramids, edges with four equivalent S(4)Pr4Zr trigonal bipyramids, and edges with four equivalent S(1)Pr2Zr2 trigonal pyramids. In the third S site, S(3) is bonded to four equivalent Pr(1) and one Zr(1) atom to form SPr4Zr square pyramids that share corners with four equivalent S(4)Pr4Zr trigonal bipyramids, corners with five equivalent S(2)Pr4Zr trigonal bipyramids, corners with eight equivalent S(1)Pr2Zr2 trigonal pyramids, edges with two equivalent S(3)Pr4Zr square pyramids,  an edgeedge with one S(4)Pr4Zr trigonal bipyramid, edges with two equivalent S(2)Pr4Zr trigonal bipyramids, edges with two equivalent S(1)Pr2Zr2 trigonal pyramids, and  a faceface with one S(4)Pr4Zr trigonal bipyramid. In the fourth S site, S(4) is bonded to four equivalent Pr(1) and one Zr(1) atom to form distorted SPr4Zr trigonal bipyramids that share corners with four equivalent S(3)Pr4Zr square pyramids,  a cornercorner with one S(2)Pr4Zr trigonal bipyramid, corners with four equivalent S(4)Pr4Zr trigonal bipyramids, corners with four equivalent S(1)Pr2Zr2 trigonal pyramids,  an edgeedge with one S(3)Pr4Zr square pyramid, edges with four equivalent S(2)Pr4Zr trigonal bipyramids, edges with four equivalent S(1)Pr2Zr2 trigonal pyramids, and  a faceface with one S(3)Pr4Zr square pyramid.
Pr2ZrS5 crystallizes in the orthorhombic Pnma space group. Pr(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There is one shorter (2.98 Å) and one longer (2.99 Å) Pr(1)-S(1) bond length. There is one shorter (2.96 Å) and one longer (3.04 Å) Pr(1)-S(2) bond length. There is one shorter (2.91 Å) and one longer (2.93 Å) Pr(1)-S(3) bond length. There is one shorter (2.92 Å) and one longer (2.95 Å) Pr(1)-S(4) bond length. Zr(1) is bonded to one S(2), one S(3), one S(4), and four equivalent S(1) atoms to form distorted edge-sharing ZrS7 pentagonal bipyramids. The Zr(1)-S(2) bond length is 2.67 Å. The Zr(1)-S(3) bond length is 2.73 Å. The Zr(1)-S(4) bond length is 2.61 Å. There are two shorter (2.55 Å) and two longer (2.71 Å) Zr(1)-S(1) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Pr(1) and two equivalent Zr(1) atoms to form distorted SPr2Zr2 trigonal pyramids that share corners with four equivalent S(3)Pr4Zr square pyramids, corners with two equivalent S(2)Pr4Zr trigonal bipyramids, corners with two equivalent S(4)Pr4Zr trigonal bipyramids, corners with six equivalent S(1)Pr2Zr2 trigonal pyramids,  an edgeedge with one S(3)Pr4Zr square pyramid, edges with two equivalent S(2)Pr4Zr trigonal bipyramids, edges with two equivalent S(4)Pr4Zr trigonal bipyramids, and  an edgeedge with one S(1)Pr2Zr2 trigonal pyramid. In the second S site, S(2) is bonded to four equivalent Pr(1) and one Zr(1) atom to form distorted SPr4Zr trigonal bipyramids that share corners with five equivalent S(3)Pr4Zr square pyramids,  a cornercorner with one S(4)Pr4Zr trigonal bipyramid, corners with four equivalent S(2)Pr4Zr trigonal bipyramids, corners with four equivalent S(1)Pr2Zr2 trigonal pyramids, edges with two equivalent S(3)Pr4Zr square pyramids, edges with four equivalent S(4)Pr4Zr trigonal bipyramids, and edges with four equivalent S(1)Pr2Zr2 trigonal pyramids. In the third S site, S(3) is bonded to four equivalent Pr(1) and one Zr(1) atom to form SPr4Zr square pyramids that share corners with four equivalent S(4)Pr4Zr trigonal bipyramids, corners with five equivalent S(2)Pr4Zr trigonal bipyramids, corners with eight equivalent S(1)Pr2Zr2 trigonal pyramids, edges with two equivalent S(3)Pr4Zr square pyramids,  an edgeedge with one S(4)Pr4Zr trigonal bipyramid, edges with two equivalent S(2)Pr4Zr trigonal bipyramids, edges with two equivalent S(1)Pr2Zr2 trigonal pyramids, and  a faceface with one S(4)Pr4Zr trigonal bipyramid. In the fourth S site, S(4) is bonded to four equivalent Pr(1) and one Zr(1) atom to form distorted SPr4Zr trigonal bipyramids that share corners with four equivalent S(3)Pr4Zr square pyramids,  a cornercorner with one S(2)Pr4Zr trigonal bipyramid, corners with four equivalent S(4)Pr4Zr trigonal bipyramids, corners with four equivalent S(1)Pr2Zr2 trigonal pyramids,  an edgeedge with one S(3)Pr4Zr square pyramid, edges with four equivalent S(2)Pr4Zr trigonal bipyramids, edges with four equivalent S(1)Pr2Zr2 trigonal pyramids, and  a faceface with one S(3)Pr4Zr square pyramid.