Y2ZrS5 crystallizes in the orthorhombic Pnma space group. Y(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 Y(1) and two equivalent Zr(1) atoms to form distorted SY2Zr2 tetrahedra that share corners with four equivalent S(3)Y4Zr square pyramids, corners with six equivalent S(1)Y2Zr2 tetrahedra, corners with two equivalent S(2)Y4Zr trigonal bipyramids, corners with two equivalent S(4)Y4Zr trigonal bipyramids,  an edgeedge with one S(3)Y4Zr square pyramid,  an edgeedge with one S(1)Y2Zr2 tetrahedra, edges with two equivalent S(2)Y4Zr trigonal bipyramids, and edges with two equivalent S(4)Y4Zr trigonal bipyramids. In the second S site, S(2) is bonded to four equivalent Y(1) and one Zr(1) atom to form distorted SY4Zr trigonal bipyramids that share corners with five equivalent S(3)Y4Zr square pyramids, corners with four equivalent S(1)Y2Zr2 tetrahedra,  a cornercorner with one S(4)Y4Zr trigonal bipyramid, corners with four equivalent S(2)Y4Zr trigonal bipyramids, edges with two equivalent S(3)Y4Zr square pyramids, edges with four equivalent S(1)Y2Zr2 tetrahedra, and edges with four equivalent S(4)Y4Zr trigonal bipyramids. In the third S site, S(3) is bonded to four equivalent Y(1) and one Zr(1) atom to form SY4Zr square pyramids that share corners with eight equivalent S(1)Y2Zr2 tetrahedra, corners with four equivalent S(4)Y4Zr trigonal bipyramids, corners with five equivalent S(2)Y4Zr trigonal bipyramids, edges with two equivalent S(3)Y4Zr square pyramids, edges with two equivalent S(1)Y2Zr2 tetrahedra,  an edgeedge with one S(4)Y4Zr trigonal bipyramid, edges with two equivalent S(2)Y4Zr trigonal bipyramids, and  a faceface with one S(4)Y4Zr trigonal bipyramid. In the fourth S site, S(4) is bonded to four equivalent Y(1) and one Zr(1) atom to form distorted SY4Zr trigonal bipyramids that share corners with four equivalent S(3)Y4Zr square pyramids, corners with four equivalent S(1)Y2Zr2 tetrahedra,  a cornercorner with one S(2)Y4Zr trigonal bipyramid, corners with four equivalent S(4)Y4Zr trigonal bipyramids,  an edgeedge with one S(3)Y4Zr square pyramid, edges with four equivalent S(1)Y2Zr2 tetrahedra, edges with four equivalent S(2)Y4Zr trigonal bipyramids, and  a faceface with one S(3)Y4Zr square pyramid.
Y2ZrS5 crystallizes in the orthorhombic Pnma space group. Y(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 (2.81 Å) and one longer (2.83 Å) Y(1)-S(1) bond length. There is one shorter (2.86 Å) and one longer (2.98 Å) Y(1)-S(2) bond length. There is one shorter (2.86 Å) and one longer (2.88 Å) Y(1)-S(3) bond length. There is one shorter (2.81 Å) and one longer (2.86 Å) Y(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 2.71 Å. The Zr(1)-S(3) bond length is 2.70 Å. The Zr(1)-S(4) bond length is 2.62 Å. There are two shorter (2.52 Å) and two longer (2.66 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 Y(1) and two equivalent Zr(1) atoms to form distorted SY2Zr2 tetrahedra that share corners with four equivalent S(3)Y4Zr square pyramids, corners with six equivalent S(1)Y2Zr2 tetrahedra, corners with two equivalent S(2)Y4Zr trigonal bipyramids, corners with two equivalent S(4)Y4Zr trigonal bipyramids,  an edgeedge with one S(3)Y4Zr square pyramid,  an edgeedge with one S(1)Y2Zr2 tetrahedra, edges with two equivalent S(2)Y4Zr trigonal bipyramids, and edges with two equivalent S(4)Y4Zr trigonal bipyramids. In the second S site, S(2) is bonded to four equivalent Y(1) and one Zr(1) atom to form distorted SY4Zr trigonal bipyramids that share corners with five equivalent S(3)Y4Zr square pyramids, corners with four equivalent S(1)Y2Zr2 tetrahedra,  a cornercorner with one S(4)Y4Zr trigonal bipyramid, corners with four equivalent S(2)Y4Zr trigonal bipyramids, edges with two equivalent S(3)Y4Zr square pyramids, edges with four equivalent S(1)Y2Zr2 tetrahedra, and edges with four equivalent S(4)Y4Zr trigonal bipyramids. In the third S site, S(3) is bonded to four equivalent Y(1) and one Zr(1) atom to form SY4Zr square pyramids that share corners with eight equivalent S(1)Y2Zr2 tetrahedra, corners with four equivalent S(4)Y4Zr trigonal bipyramids, corners with five equivalent S(2)Y4Zr trigonal bipyramids, edges with two equivalent S(3)Y4Zr square pyramids, edges with two equivalent S(1)Y2Zr2 tetrahedra,  an edgeedge with one S(4)Y4Zr trigonal bipyramid, edges with two equivalent S(2)Y4Zr trigonal bipyramids, and  a faceface with one S(4)Y4Zr trigonal bipyramid. In the fourth S site, S(4) is bonded to four equivalent Y(1) and one Zr(1) atom to form distorted SY4Zr trigonal bipyramids that share corners with four equivalent S(3)Y4Zr square pyramids, corners with four equivalent S(1)Y2Zr2 tetrahedra,  a cornercorner with one S(2)Y4Zr trigonal bipyramid, corners with four equivalent S(4)Y4Zr trigonal bipyramids,  an edgeedge with one S(3)Y4Zr square pyramid, edges with four equivalent S(1)Y2Zr2 tetrahedra, edges with four equivalent S(2)Y4Zr trigonal bipyramids, and  a faceface with one S(3)Y4Zr square pyramid.