Yb3InS6 crystallizes in the orthorhombic P2_12_12 space group. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 8-coordinate geometry to one S(1), one S(6), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. In the second Yb site, Yb(2) is bonded in a 8-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. In the third Yb site, Yb(3) is bonded to one S(3), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form YbS6 octahedra that share  a cornercorner with one In(2)S6 octahedra, edges with two equivalent Yb(3)S6 octahedra, and edges with two equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are two inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(2) and four equivalent S(6) atoms to form InS6 octahedra that share edges with two equivalent In(1)S6 octahedra and edges with four equivalent Yb(3)S6 octahedra. In the second In site, In(2) is bonded to two equivalent S(3) and four equivalent S(1) atoms to form InS6 octahedra that share corners with two equivalent Yb(3)S6 octahedra and edges with two equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Yb(2), two equivalent Yb(1), and two equivalent Yb(3) atoms to form distorted SYb5 trigonal bipyramids that share  a cornercorner with one S(6)Yb3In2 trigonal bipyramid, corners with four equivalent S(2)Yb4In trigonal bipyramids, edges with two equivalent S(1)Yb3In2 square pyramids,  an edgeedge with one S(2)Yb4In trigonal bipyramid, edges with two equivalent S(6)Yb3In2 trigonal bipyramids, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the second S site, S(6) is bonded to one Yb(1), one Yb(2), one Yb(3), and two equivalent In(1) atoms to form distorted SYb3In2 trigonal bipyramids that share corners with three equivalent S(1)Yb3In2 square pyramids,  a cornercorner with one S(5)Yb5 trigonal bipyramid, corners with four equivalent S(6)Yb3In2 trigonal bipyramids,  an edgeedge with one S(6)Yb3In2 trigonal bipyramid, edges with two equivalent S(5)Yb5 trigonal bipyramids, and edges with four equivalent S(2)Yb4In trigonal bipyramids. In the third S site, S(1) is bonded to one Yb(1), two equivalent Yb(2), and two equivalent In(2) atoms to form distorted SYb3In2 square pyramids that share corners with two equivalent S(1)Yb3In2 square pyramids, corners with two equivalent S(2)Yb4In trigonal bipyramids, corners with three equivalent S(6)Yb3In2 trigonal bipyramids, edges with three equivalent S(1)Yb3In2 square pyramids,  an edgeedge with one S(2)Yb4In trigonal bipyramid, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the fourth S site, S(2) is bonded to two equivalent Yb(2), two equivalent Yb(3), and one In(1) atom to form SYb4In trigonal bipyramids that share corners with two equivalent S(1)Yb3In2 square pyramids,  a cornercorner with one S(2)Yb4In trigonal bipyramid, corners with four equivalent S(5)Yb5 trigonal bipyramids,  an edgeedge with one S(1)Yb3In2 square pyramid,  an edgeedge with one S(5)Yb5 trigonal bipyramid, edges with two equivalent S(2)Yb4In trigonal bipyramids, and edges with four equivalent S(6)Yb3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded in a 5-coordinate geometry to one Yb(3), two equivalent Yb(1), one In(2), and one S(4) atom. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Yb(1), two equivalent Yb(2), and one S(3) atom.
Yb3InS6 crystallizes in the orthorhombic P2_12_12 space group. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 8-coordinate geometry to one S(1), one S(6), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. The Yb(1)-S(1) bond length is 2.84 Å. The Yb(1)-S(6) bond length is 2.83 Å. There is one shorter (2.90 Å) and one longer (3.24 Å) Yb(1)-S(3) bond length. There is one shorter (2.86 Å) and one longer (2.91 Å) Yb(1)-S(4) bond length. There is one shorter (2.77 Å) and one longer (2.79 Å) Yb(1)-S(5) bond length. In the second Yb site, Yb(2) is bonded in a 8-coordinate geometry to one S(5), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. The Yb(2)-S(5) bond length is 2.81 Å. The Yb(2)-S(6) bond length is 3.10 Å. There is one shorter (3.12 Å) and one longer (3.33 Å) Yb(2)-S(1) bond length. There is one shorter (2.83 Å) and one longer (2.84 Å) Yb(2)-S(2) bond length. There is one shorter (3.02 Å) and one longer (3.07 Å) Yb(2)-S(4) bond length. In the third Yb site, Yb(3) is bonded to one S(3), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form YbS6 octahedra that share  a cornercorner with one In(2)S6 octahedra, edges with two equivalent Yb(3)S6 octahedra, and edges with two equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Yb(3)-S(3) bond length is 2.78 Å. The Yb(3)-S(6) bond length is 2.82 Å. There is one shorter (2.82 Å) and one longer (2.86 Å) Yb(3)-S(2) bond length. There is one shorter (2.77 Å) and one longer (2.79 Å) Yb(3)-S(5) bond length. There are two inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(2) and four equivalent S(6) atoms to form InS6 octahedra that share edges with two equivalent In(1)S6 octahedra and edges with four equivalent Yb(3)S6 octahedra. Both In(1)-S(2) bond lengths are 2.67 Å. There are two shorter (2.61 Å) and two longer (2.64 Å) In(1)-S(6) bond lengths. In the second In site, In(2) is bonded to two equivalent S(3) and four equivalent S(1) atoms to form InS6 octahedra that share corners with two equivalent Yb(3)S6 octahedra and edges with two equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles are 54°. Both In(2)-S(3) bond lengths are 2.95 Å. There are two shorter (2.61 Å) and two longer (2.63 Å) In(2)-S(1) bond lengths. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Yb(2), two equivalent Yb(1), and two equivalent Yb(3) atoms to form distorted SYb5 trigonal bipyramids that share  a cornercorner with one S(6)Yb3In2 trigonal bipyramid, corners with four equivalent S(2)Yb4In trigonal bipyramids, edges with two equivalent S(1)Yb3In2 square pyramids,  an edgeedge with one S(2)Yb4In trigonal bipyramid, edges with two equivalent S(6)Yb3In2 trigonal bipyramids, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the second S site, S(6) is bonded to one Yb(1), one Yb(2), one Yb(3), and two equivalent In(1) atoms to form distorted SYb3In2 trigonal bipyramids that share corners with three equivalent S(1)Yb3In2 square pyramids,  a cornercorner with one S(5)Yb5 trigonal bipyramid, corners with four equivalent S(6)Yb3In2 trigonal bipyramids,  an edgeedge with one S(6)Yb3In2 trigonal bipyramid, edges with two equivalent S(5)Yb5 trigonal bipyramids, and edges with four equivalent S(2)Yb4In trigonal bipyramids. In the third S site, S(1) is bonded to one Yb(1), two equivalent Yb(2), and two equivalent In(2) atoms to form distorted SYb3In2 square pyramids that share corners with two equivalent S(1)Yb3In2 square pyramids, corners with two equivalent S(2)Yb4In trigonal bipyramids, corners with three equivalent S(6)Yb3In2 trigonal bipyramids, edges with three equivalent S(1)Yb3In2 square pyramids,  an edgeedge with one S(2)Yb4In trigonal bipyramid, and edges with two equivalent S(5)Yb5 trigonal bipyramids. In the fourth S site, S(2) is bonded to two equivalent Yb(2), two equivalent Yb(3), and one In(1) atom to form SYb4In trigonal bipyramids that share corners with two equivalent S(1)Yb3In2 square pyramids,  a cornercorner with one S(2)Yb4In trigonal bipyramid, corners with four equivalent S(5)Yb5 trigonal bipyramids,  an edgeedge with one S(1)Yb3In2 square pyramid,  an edgeedge with one S(5)Yb5 trigonal bipyramid, edges with two equivalent S(2)Yb4In trigonal bipyramids, and edges with four equivalent S(6)Yb3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded in a 5-coordinate geometry to one Yb(3), two equivalent Yb(1), one In(2), and one S(4) atom. The S(3)-S(4) bond length is 2.08 Å. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Yb(1), two equivalent Yb(2), and one S(3) atom.