Sc3InS6 crystallizes in the orthorhombic P2_12_12 space group. There are three inequivalent Sc sites. In the first Sc site, Sc(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 Sc site, Sc(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 Sc site, Sc(3) is bonded to one S(3), one S(4), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form distorted ScS7 pentagonal bipyramids that share edges with two equivalent In(1)S6 octahedra and edges with two equivalent Sc(3)S7 pentagonal bipyramids. 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 Sc(3)S7 pentagonal bipyramids. In the second In site, In(2) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(1) atoms. There are six inequivalent S sites. In the first S site, S(5) is bonded in a 5-coordinate geometry to one Sc(2), two equivalent Sc(1), and two equivalent Sc(3) atoms. In the second S site, S(6) is bonded to one Sc(1), one Sc(2), one Sc(3), and two equivalent In(1) atoms to form SSc3In2 trigonal bipyramids that share corners with three equivalent S(1)Sc3In2 trigonal bipyramids, corners with four equivalent S(6)Sc3In2 trigonal bipyramids, corners with three equivalent S(3)Sc3In trigonal pyramids, edges with four equivalent S(2)Sc4In square pyramids, and  an edgeedge with one S(6)Sc3In2 trigonal bipyramid. In the third S site, S(1) is bonded to one Sc(1), two equivalent Sc(2), and two equivalent In(2) atoms to form distorted SSc3In2 trigonal bipyramids that share corners with two equivalent S(2)Sc4In square pyramids, corners with two equivalent S(1)Sc3In2 trigonal bipyramids, corners with three equivalent S(6)Sc3In2 trigonal bipyramids, corners with two equivalent S(3)Sc3In trigonal pyramids,  an edgeedge with one S(2)Sc4In square pyramid, edges with three equivalent S(1)Sc3In2 trigonal bipyramids, and edges with two equivalent S(3)Sc3In trigonal pyramids. In the fourth S site, S(2) is bonded to two equivalent Sc(2), two equivalent Sc(3), and one In(1) atom to form SSc4In square pyramids that share  a cornercorner with one S(2)Sc4In square pyramid, corners with two equivalent S(1)Sc3In2 trigonal bipyramids, corners with two equivalent S(3)Sc3In trigonal pyramids, edges with two equivalent S(2)Sc4In square pyramids,  an edgeedge with one S(1)Sc3In2 trigonal bipyramid, and edges with four equivalent S(6)Sc3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded to one Sc(3), two equivalent Sc(1), and one In(2) atom to form distorted SSc3In trigonal pyramids that share corners with two equivalent S(2)Sc4In square pyramids, corners with two equivalent S(1)Sc3In2 trigonal bipyramids, corners with three equivalent S(6)Sc3In2 trigonal bipyramids, corners with three equivalent S(3)Sc3In trigonal pyramids, and edges with two equivalent S(1)Sc3In2 trigonal bipyramids. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to one Sc(3), two equivalent Sc(1), and two equivalent Sc(2) atoms.
Sc3InS6 crystallizes in the orthorhombic P2_12_12 space group. There are three inequivalent Sc sites. In the first Sc site, Sc(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 Sc(1)-S(1) bond length is 2.74 Å. The Sc(1)-S(6) bond length is 2.66 Å. There is one shorter (2.66 Å) and one longer (2.68 Å) Sc(1)-S(3) bond length. There is one shorter (2.76 Å) and one longer (2.81 Å) Sc(1)-S(4) bond length. There is one shorter (2.73 Å) and one longer (2.75 Å) Sc(1)-S(5) bond length. In the second Sc site, Sc(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 Sc(2)-S(5) bond length is 2.89 Å. The Sc(2)-S(6) bond length is 2.90 Å. There is one shorter (2.66 Å) and one longer (2.68 Å) Sc(2)-S(1) bond length. There is one shorter (2.90 Å) and one longer (2.98 Å) Sc(2)-S(2) bond length. There is one shorter (2.61 Å) and one longer (2.64 Å) Sc(2)-S(4) bond length. In the third Sc site, Sc(3) is bonded to one S(3), one S(4), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form distorted ScS7 pentagonal bipyramids that share edges with two equivalent In(1)S6 octahedra and edges with two equivalent Sc(3)S7 pentagonal bipyramids. The Sc(3)-S(3) bond length is 2.59 Å. The Sc(3)-S(4) bond length is 2.79 Å. The Sc(3)-S(6) bond length is 2.79 Å. Both Sc(3)-S(2) bond lengths are 2.70 Å. There is one shorter (2.61 Å) and one longer (2.62 Å) Sc(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 Sc(3)S7 pentagonal bipyramids. Both In(1)-S(2) bond lengths are 2.58 Å. All In(1)-S(6) bond lengths are 2.57 Å. In the second In site, In(2) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(1) atoms. Both In(2)-S(3) bond lengths are 2.46 Å. There are two shorter (2.56 Å) and two longer (3.02 Å) In(2)-S(1) bond lengths. There are six inequivalent S sites. In the first S site, S(5) is bonded in a 5-coordinate geometry to one Sc(2), two equivalent Sc(1), and two equivalent Sc(3) atoms. In the second S site, S(6) is bonded to one Sc(1), one Sc(2), one Sc(3), and two equivalent In(1) atoms to form SSc3In2 trigonal bipyramids that share corners with three equivalent S(1)Sc3In2 trigonal bipyramids, corners with four equivalent S(6)Sc3In2 trigonal bipyramids, corners with three equivalent S(3)Sc3In trigonal pyramids, edges with four equivalent S(2)Sc4In square pyramids, and  an edgeedge with one S(6)Sc3In2 trigonal bipyramid. In the third S site, S(1) is bonded to one Sc(1), two equivalent Sc(2), and two equivalent In(2) atoms to form distorted SSc3In2 trigonal bipyramids that share corners with two equivalent S(2)Sc4In square pyramids, corners with two equivalent S(1)Sc3In2 trigonal bipyramids, corners with three equivalent S(6)Sc3In2 trigonal bipyramids, corners with two equivalent S(3)Sc3In trigonal pyramids,  an edgeedge with one S(2)Sc4In square pyramid, edges with three equivalent S(1)Sc3In2 trigonal bipyramids, and edges with two equivalent S(3)Sc3In trigonal pyramids. In the fourth S site, S(2) is bonded to two equivalent Sc(2), two equivalent Sc(3), and one In(1) atom to form SSc4In square pyramids that share  a cornercorner with one S(2)Sc4In square pyramid, corners with two equivalent S(1)Sc3In2 trigonal bipyramids, corners with two equivalent S(3)Sc3In trigonal pyramids, edges with two equivalent S(2)Sc4In square pyramids,  an edgeedge with one S(1)Sc3In2 trigonal bipyramid, and edges with four equivalent S(6)Sc3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded to one Sc(3), two equivalent Sc(1), and one In(2) atom to form distorted SSc3In trigonal pyramids that share corners with two equivalent S(2)Sc4In square pyramids, corners with two equivalent S(1)Sc3In2 trigonal bipyramids, corners with three equivalent S(6)Sc3In2 trigonal bipyramids, corners with three equivalent S(3)Sc3In trigonal pyramids, and edges with two equivalent S(1)Sc3In2 trigonal bipyramids. In the sixth S site, S(4) is bonded in a 5-coordinate geometry to one Sc(3), two equivalent Sc(1), and two equivalent Sc(2) atoms.