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 distorted YbS6 octahedra that share corners with two equivalent S(6)Yb4S square pyramids and  a cornercorner with one S(5)Yb3S tetrahedra. In the second Yb site, Yb(2) is bonded in a 6-coordinate geometry to one S(1), one S(5), two equivalent S(2), and two equivalent S(4) atoms. In the third Yb site, Yb(3) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(4), two equivalent S(2), and two equivalent S(6) atoms. In the fourth Yb site, Yb(4) is bonded in a 7-coordinate geometry to one S(1), one S(4), one S(5), two equivalent S(2), and two equivalent S(6) atoms. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Yb(2), two equivalent Yb(4), and one S(3) atom to form distorted SYb3S tetrahedra that share  a cornercorner with one Yb(1)S6 octahedra and corners with four equivalent S(6)Yb4S square pyramids. The corner-sharing octahedral tilt angles are 71°. In the second S site, S(6) is bonded to two equivalent Yb(3), two equivalent Yb(4), and one S(4) atom to form distorted SYb4S square pyramids that share  a cornercorner with one Yb(1)S6 octahedra, corners with two equivalent S(3)Yb3S tetrahedra, corners with two equivalent S(5)Yb3S tetrahedra, and edges with two equivalent S(6)Yb4S square pyramids. The corner-sharing octahedral tilt angles are 55°. In the third S site, S(1) is bonded in a 6-coordinate geometry to one Yb(1), one Yb(2), two equivalent Yb(3), and two equivalent Yb(4) atoms. In the fourth S site, S(2) is bonded in a 6-coordinate geometry to one Yb(1), one Yb(2), two equivalent Yb(3), and two equivalent Yb(4) atoms. In the fifth S site, S(3) is bonded to one Yb(1), two equivalent Yb(3), and one S(5) atom to form corner-sharing SYb3S tetrahedra. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to one Yb(1), one Yb(2), one Yb(3), one Yb(4), and one S(6) atom.
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 distorted YbS6 octahedra that share corners with two equivalent S(6)Yb4S square pyramids and  a cornercorner with one S(5)Yb3S tetrahedra. The Yb(1)-S(1) bond length is 2.74 Å. The Yb(1)-S(3) bond length is 2.66 Å. Both Yb(1)-S(2) bond lengths are 3.02 Å. Both Yb(1)-S(4) bond lengths are 2.87 Å. In the second Yb site, Yb(2) is bonded in a 6-coordinate geometry to one S(1), one S(5), two equivalent S(2), and two equivalent S(4) atoms. The Yb(2)-S(1) bond length is 3.09 Å. The Yb(2)-S(5) bond length is 2.69 Å. Both Yb(2)-S(2) bond lengths are 2.87 Å. Both Yb(2)-S(4) bond lengths are 2.90 Å. In the third Yb site, Yb(3) is bonded in a 7-coordinate geometry to one S(1), one S(3), one S(4), two equivalent S(2), and two equivalent S(6) atoms. The Yb(3)-S(1) bond length is 3.04 Å. The Yb(3)-S(3) bond length is 2.69 Å. The Yb(3)-S(4) bond length is 2.85 Å. There is one shorter (2.92 Å) and one longer (3.08 Å) Yb(3)-S(2) bond length. There is one shorter (2.84 Å) and one longer (2.95 Å) Yb(3)-S(6) bond length. In the fourth Yb site, Yb(4) is bonded in a 7-coordinate geometry to one S(1), one S(4), one S(5), two equivalent S(2), and two equivalent S(6) atoms. The Yb(4)-S(1) bond length is 3.03 Å. The Yb(4)-S(4) bond length is 2.90 Å. The Yb(4)-S(5) bond length is 2.77 Å. There is one shorter (2.92 Å) and one longer (2.94 Å) Yb(4)-S(2) bond length. There is one shorter (2.81 Å) and one longer (2.91 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(4), and one S(3) atom to form distorted SYb3S tetrahedra that share  a cornercorner with one Yb(1)S6 octahedra and corners with four equivalent S(6)Yb4S square pyramids. The corner-sharing octahedral tilt angles are 71°. The S(5)-S(3) bond length is 2.10 Å. In the second S site, S(6) is bonded to two equivalent Yb(3), two equivalent Yb(4), and one S(4) atom to form distorted SYb4S square pyramids that share  a cornercorner with one Yb(1)S6 octahedra, corners with two equivalent S(3)Yb3S tetrahedra, corners with two equivalent S(5)Yb3S tetrahedra, and edges with two equivalent S(6)Yb4S square pyramids. The corner-sharing octahedral tilt angles are 55°. The S(6)-S(4) bond length is 2.11 Å. In the third S site, S(1) is bonded in a 6-coordinate geometry to one Yb(1), one Yb(2), two equivalent Yb(3), and two equivalent Yb(4) atoms. In the fourth S site, S(2) is bonded in a 6-coordinate geometry to one Yb(1), one Yb(2), two equivalent Yb(3), and two equivalent Yb(4) atoms. In the fifth S site, S(3) is bonded to one Yb(1), two equivalent Yb(3), and one S(5) atom to form corner-sharing SYb3S tetrahedra. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to one Yb(1), one Yb(2), one Yb(3), one Yb(4), and one S(6) atom.