Yb2S3 crystallizes in the orthorhombic Cmc2_1 space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of distorted face, edge, and corner-sharing YbS6 octahedra. In the second Yb site, Yb(2) is bonded to one S(3), one S(5), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of distorted face, edge, and corner-sharing YbS6 octahedra. In the third Yb site, Yb(3) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(5), two equivalent S(4), and two equivalent S(6) atoms. In the fourth Yb site, Yb(4) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(6) atoms to form distorted YbS6 pentagonal pyramids that share  a cornercorner with one Yb(2)S6 octahedra, corners with three equivalent Yb(1)S6 octahedra, corners with two equivalent S(4)Yb4S square pyramids,  an edgeedge with one Yb(2)S6 octahedra, and edges with three equivalent Yb(4)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 51-74°. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Yb(2), two equivalent Yb(3), and two equivalent Yb(4) atoms to form distorted SYb5 trigonal bipyramids that share corners with two equivalent S(4)Yb4S square pyramids, corners with two equivalent S(2)Yb4 trigonal pyramids, edges with two equivalent S(4)Yb4S square pyramids, edges with two equivalent S(1)Yb5 trigonal bipyramids, and edges with two equivalent S(2)Yb4 trigonal pyramids. In the second S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Yb(3), two equivalent Yb(4), and one S(4) atom. In the third S site, S(1) is bonded to one Yb(1), two equivalent Yb(3), and two equivalent Yb(4) atoms to form distorted SYb5 trigonal bipyramids that share corners with two equivalent S(4)Yb4S square pyramids, corners with six equivalent S(2)Yb4 trigonal pyramids, edges with two equivalent S(4)Yb4S square pyramids, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the fourth S site, S(2) is bonded to one Yb(1), one Yb(2), and two equivalent Yb(4) atoms to form distorted SYb4 trigonal pyramids that share corners with four equivalent S(4)Yb4S square pyramids,  a cornercorner with one S(5)Yb5 trigonal bipyramid, corners with three equivalent S(1)Yb5 trigonal bipyramids, corners with two equivalent S(2)Yb4 trigonal pyramids,  an edgeedge with one S(5)Yb5 trigonal bipyramid, and  an edgeedge with one S(2)Yb4 trigonal pyramid. In the fifth S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Yb(1), one Yb(2), and two equivalent Yb(3) atoms. In the sixth S site, S(4) is bonded to one Yb(1), one Yb(2), two equivalent Yb(3), and one S(6) atom to form distorted SYb4S square pyramids that share corners with two equivalent Yb(4)S6 pentagonal pyramids, corners with two equivalent S(4)Yb4S square pyramids,  a cornercorner with one S(1)Yb5 trigonal bipyramid,  a cornercorner with one S(5)Yb5 trigonal bipyramid, corners with four equivalent S(2)Yb4 trigonal pyramids,  an edgeedge with one S(4)Yb4S square pyramid,  an edgeedge with one S(1)Yb5 trigonal bipyramid, and  an edgeedge with one S(5)Yb5 trigonal bipyramid.
Yb2S3 crystallizes in the orthorhombic Cmc2_1 space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of distorted face, edge, and corner-sharing YbS6 octahedra. The Yb(1)-S(1) bond length is 2.82 Å. The Yb(1)-S(3) bond length is 2.85 Å. Both Yb(1)-S(2) bond lengths are 2.71 Å. Both Yb(1)-S(4) bond lengths are 2.83 Å. In the second Yb site, Yb(2) is bonded to one S(3), one S(5), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of distorted face, edge, and corner-sharing YbS6 octahedra. The Yb(2)-S(3) bond length is 2.79 Å. The Yb(2)-S(5) bond length is 2.72 Å. Both Yb(2)-S(2) bond lengths are 2.97 Å. Both Yb(2)-S(4) bond lengths are 2.99 Å. In the third Yb site, Yb(3) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(5), two equivalent S(4), and two equivalent S(6) atoms. The Yb(3)-S(1) bond length is 2.82 Å. The Yb(3)-S(3) bond length is 2.96 Å. The Yb(3)-S(5) bond length is 2.77 Å. There is one shorter (2.81 Å) and one longer (2.83 Å) Yb(3)-S(4) bond length. There is one shorter (2.84 Å) and one longer (3.01 Å) Yb(3)-S(6) bond length. In the fourth Yb site, Yb(4) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(6) atoms to form distorted YbS6 pentagonal pyramids that share  a cornercorner with one Yb(2)S6 octahedra, corners with three equivalent Yb(1)S6 octahedra, corners with two equivalent S(4)Yb4S square pyramids,  an edgeedge with one Yb(2)S6 octahedra, and edges with three equivalent Yb(4)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 51-74°. The Yb(4)-S(1) bond length is 2.82 Å. The Yb(4)-S(5) bond length is 2.75 Å. There is one shorter (2.77 Å) and one longer (2.78 Å) Yb(4)-S(2) bond length. There is one shorter (3.03 Å) and one longer (3.04 Å) Yb(4)-S(6) bond length. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Yb(2), two equivalent Yb(3), and two equivalent Yb(4) atoms to form distorted SYb5 trigonal bipyramids that share corners with two equivalent S(4)Yb4S square pyramids, corners with two equivalent S(2)Yb4 trigonal pyramids, edges with two equivalent S(4)Yb4S square pyramids, edges with two equivalent S(1)Yb5 trigonal bipyramids, and edges with two equivalent S(2)Yb4 trigonal pyramids. In the second S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Yb(3), two equivalent Yb(4), and one S(4) atom. The S(6)-S(4) bond length is 2.06 Å. In the third S site, S(1) is bonded to one Yb(1), two equivalent Yb(3), and two equivalent Yb(4) atoms to form distorted SYb5 trigonal bipyramids that share corners with two equivalent S(4)Yb4S square pyramids, corners with six equivalent S(2)Yb4 trigonal pyramids, edges with two equivalent S(4)Yb4S square pyramids, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the fourth S site, S(2) is bonded to one Yb(1), one Yb(2), and two equivalent Yb(4) atoms to form distorted SYb4 trigonal pyramids that share corners with four equivalent S(4)Yb4S square pyramids,  a cornercorner with one S(5)Yb5 trigonal bipyramid, corners with three equivalent S(1)Yb5 trigonal bipyramids, corners with two equivalent S(2)Yb4 trigonal pyramids,  an edgeedge with one S(5)Yb5 trigonal bipyramid, and  an edgeedge with one S(2)Yb4 trigonal pyramid. In the fifth S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Yb(1), one Yb(2), and two equivalent Yb(3) atoms. In the sixth S site, S(4) is bonded to one Yb(1), one Yb(2), two equivalent Yb(3), and one S(6) atom to form distorted SYb4S square pyramids that share corners with two equivalent Yb(4)S6 pentagonal pyramids, corners with two equivalent S(4)Yb4S square pyramids,  a cornercorner with one S(1)Yb5 trigonal bipyramid,  a cornercorner with one S(5)Yb5 trigonal bipyramid, corners with four equivalent S(2)Yb4 trigonal pyramids,  an edgeedge with one S(4)Yb4S square pyramid,  an edgeedge with one S(1)Yb5 trigonal bipyramid, and  an edgeedge with one S(5)Yb5 trigonal bipyramid.