Sm3InS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Sm sites. In the first Sm site, Sm(1) is bonded to one S(1), one S(3), one S(6), two equivalent S(2), and two equivalent S(4) atoms to form distorted SmS7 pentagonal bipyramids that share  a cornercorner with one In(1)S6 octahedra, edges with two equivalent In(2)S6 octahedra, and edges with two equivalent Sm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 40°. In the second Sm site, Sm(2) is bonded in a 8-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. In the third Sm site, Sm(3) is bonded in a 8-coordinate geometry to one S(1), one S(5), two equivalent S(3), two equivalent S(4), and two equivalent S(6) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(3) and four equivalent S(5) atoms to form InS6 octahedra that share corners with two equivalent Sm(1)S7 pentagonal bipyramids and edges with two equivalent In(1)S6 octahedra. In the second In site, In(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form InS6 octahedra that share edges with two equivalent In(2)S6 octahedra and edges with four equivalent Sm(1)S7 pentagonal bipyramids. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Sm(3), two equivalent Sm(2), and two equivalent In(1) atoms to form SSm3In2 trigonal bipyramids that share corners with two equivalent S(2)Sm4In square pyramids, corners with two equivalent S(5)Sm3In2 trigonal bipyramids, corners with three equivalent S(1)Sm3In2 trigonal bipyramids, corners with four equivalent S(6)Sm5 trigonal bipyramids, corners with two equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(2)Sm4In square pyramid,  an edgeedge with one S(6)Sm5 trigonal bipyramid, edges with two equivalent S(4)Sm5 trigonal bipyramids, edges with three equivalent S(5)Sm3In2 trigonal bipyramids, and edges with two equivalent S(3)Sm3In trigonal pyramids. In the second S site, S(6) is bonded to one Sm(1), two equivalent Sm(2), and two equivalent Sm(3) atoms to form distorted SSm5 trigonal bipyramids that share corners with four equivalent S(2)Sm4In square pyramids,  a cornercorner with one S(1)Sm3In2 trigonal bipyramid, corners with two equivalent S(4)Sm5 trigonal bipyramids, corners with four equivalent S(5)Sm3In2 trigonal bipyramids, corners with two equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(2)Sm4In square pyramid,  an edgeedge with one S(5)Sm3In2 trigonal bipyramid, edges with two equivalent S(1)Sm3In2 trigonal bipyramids, edges with two equivalent S(6)Sm5 trigonal bipyramids, edges with three equivalent S(4)Sm5 trigonal bipyramids, and  a faceface with one S(3)Sm3In trigonal pyramid. In the third S site, S(1) is bonded to one Sm(1), one Sm(2), one Sm(3), and two equivalent In(2) atoms to form distorted SSm3In2 trigonal bipyramids that share  a cornercorner with one S(4)Sm5 trigonal bipyramid,  a cornercorner with one S(6)Sm5 trigonal bipyramid, corners with three equivalent S(5)Sm3In2 trigonal bipyramids, corners with four equivalent S(1)Sm3In2 trigonal bipyramids, corners with three equivalent S(3)Sm3In trigonal pyramids, edges with four equivalent S(2)Sm4In square pyramids,  an edgeedge with one S(1)Sm3In2 trigonal bipyramid, edges with two equivalent S(4)Sm5 trigonal bipyramids, and edges with two equivalent S(6)Sm5 trigonal bipyramids. In the fourth S site, S(2) is bonded to two equivalent Sm(1), two equivalent Sm(2), and one In(2) atom to form SSm4In square pyramids that share  a cornercorner with one S(2)Sm4In square pyramid, corners with two equivalent S(5)Sm3In2 trigonal bipyramids, corners with four equivalent S(4)Sm5 trigonal bipyramids, corners with four equivalent S(6)Sm5 trigonal bipyramids, corners with two equivalent S(3)Sm3In trigonal pyramids, edges with two equivalent S(2)Sm4In square pyramids,  an edgeedge with one S(5)Sm3In2 trigonal bipyramid,  an edgeedge with one S(4)Sm5 trigonal bipyramid,  an edgeedge with one S(6)Sm5 trigonal bipyramid, and edges with four equivalent S(1)Sm3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded to one Sm(1), two equivalent Sm(3), and one In(1) atom to form distorted SSm3In trigonal pyramids that share corners with two equivalent S(2)Sm4In square pyramids, corners with two equivalent S(5)Sm3In2 trigonal bipyramids, corners with two equivalent S(6)Sm5 trigonal bipyramids, corners with three equivalent S(1)Sm3In2 trigonal bipyramids, corners with four equivalent S(4)Sm5 trigonal bipyramids, corners with three equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(4)Sm5 trigonal bipyramid, edges with two equivalent S(5)Sm3In2 trigonal bipyramids, and  a faceface with one S(6)Sm5 trigonal bipyramid. In the sixth S site, S(4) is bonded to one Sm(2), two equivalent Sm(1), and two equivalent Sm(3) atoms to form distorted SSm5 trigonal bipyramids that share corners with four equivalent S(2)Sm4In square pyramids,  a cornercorner with one S(1)Sm3In2 trigonal bipyramid, corners with two equivalent S(6)Sm5 trigonal bipyramids, corners with four equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(2)Sm4In square pyramid, edges with two equivalent S(1)Sm3In2 trigonal bipyramids, edges with two equivalent S(5)Sm3In2 trigonal bipyramids, edges with two equivalent S(4)Sm5 trigonal bipyramids, edges with three equivalent S(6)Sm5 trigonal bipyramids, and  an edgeedge with one S(3)Sm3In trigonal pyramid.
Sm3InS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Sm sites. In the first Sm site, Sm(1) is bonded to one S(1), one S(3), one S(6), two equivalent S(2), and two equivalent S(4) atoms to form distorted SmS7 pentagonal bipyramids that share  a cornercorner with one In(1)S6 octahedra, edges with two equivalent In(2)S6 octahedra, and edges with two equivalent Sm(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 40°. The Sm(1)-S(1) bond length is 2.96 Å. The Sm(1)-S(3) bond length is 2.78 Å. The Sm(1)-S(6) bond length is 2.93 Å. Both Sm(1)-S(2) bond lengths are 2.87 Å. Both Sm(1)-S(4) bond lengths are 2.79 Å. In the second Sm site, Sm(2) is bonded in a 8-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. The Sm(2)-S(1) bond length is 3.16 Å. The Sm(2)-S(4) bond length is 3.08 Å. Both Sm(2)-S(2) bond lengths are 3.00 Å. Both Sm(2)-S(5) bond lengths are 2.90 Å. Both Sm(2)-S(6) bond lengths are 2.82 Å. In the third Sm site, Sm(3) is bonded in a 8-coordinate geometry to one S(1), one S(5), two equivalent S(3), two equivalent S(4), and two equivalent S(6) atoms. The Sm(3)-S(1) bond length is 2.90 Å. The Sm(3)-S(5) bond length is 2.96 Å. Both Sm(3)-S(3) bond lengths are 2.84 Å. Both Sm(3)-S(4) bond lengths are 2.90 Å. Both Sm(3)-S(6) bond lengths are 2.95 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(3) and four equivalent S(5) atoms to form InS6 octahedra that share corners with two equivalent Sm(1)S7 pentagonal bipyramids and edges with two equivalent In(1)S6 octahedra. Both In(1)-S(3) bond lengths are 2.45 Å. All In(1)-S(5) bond lengths are 2.74 Å. In the second In site, In(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form InS6 octahedra that share edges with two equivalent In(2)S6 octahedra and edges with four equivalent Sm(1)S7 pentagonal bipyramids. Both In(2)-S(2) bond lengths are 2.62 Å. All In(2)-S(1) bond lengths are 2.62 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Sm(3), two equivalent Sm(2), and two equivalent In(1) atoms to form SSm3In2 trigonal bipyramids that share corners with two equivalent S(2)Sm4In square pyramids, corners with two equivalent S(5)Sm3In2 trigonal bipyramids, corners with three equivalent S(1)Sm3In2 trigonal bipyramids, corners with four equivalent S(6)Sm5 trigonal bipyramids, corners with two equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(2)Sm4In square pyramid,  an edgeedge with one S(6)Sm5 trigonal bipyramid, edges with two equivalent S(4)Sm5 trigonal bipyramids, edges with three equivalent S(5)Sm3In2 trigonal bipyramids, and edges with two equivalent S(3)Sm3In trigonal pyramids. In the second S site, S(6) is bonded to one Sm(1), two equivalent Sm(2), and two equivalent Sm(3) atoms to form distorted SSm5 trigonal bipyramids that share corners with four equivalent S(2)Sm4In square pyramids,  a cornercorner with one S(1)Sm3In2 trigonal bipyramid, corners with two equivalent S(4)Sm5 trigonal bipyramids, corners with four equivalent S(5)Sm3In2 trigonal bipyramids, corners with two equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(2)Sm4In square pyramid,  an edgeedge with one S(5)Sm3In2 trigonal bipyramid, edges with two equivalent S(1)Sm3In2 trigonal bipyramids, edges with two equivalent S(6)Sm5 trigonal bipyramids, edges with three equivalent S(4)Sm5 trigonal bipyramids, and  a faceface with one S(3)Sm3In trigonal pyramid. In the third S site, S(1) is bonded to one Sm(1), one Sm(2), one Sm(3), and two equivalent In(2) atoms to form distorted SSm3In2 trigonal bipyramids that share  a cornercorner with one S(4)Sm5 trigonal bipyramid,  a cornercorner with one S(6)Sm5 trigonal bipyramid, corners with three equivalent S(5)Sm3In2 trigonal bipyramids, corners with four equivalent S(1)Sm3In2 trigonal bipyramids, corners with three equivalent S(3)Sm3In trigonal pyramids, edges with four equivalent S(2)Sm4In square pyramids,  an edgeedge with one S(1)Sm3In2 trigonal bipyramid, edges with two equivalent S(4)Sm5 trigonal bipyramids, and edges with two equivalent S(6)Sm5 trigonal bipyramids. In the fourth S site, S(2) is bonded to two equivalent Sm(1), two equivalent Sm(2), and one In(2) atom to form SSm4In square pyramids that share  a cornercorner with one S(2)Sm4In square pyramid, corners with two equivalent S(5)Sm3In2 trigonal bipyramids, corners with four equivalent S(4)Sm5 trigonal bipyramids, corners with four equivalent S(6)Sm5 trigonal bipyramids, corners with two equivalent S(3)Sm3In trigonal pyramids, edges with two equivalent S(2)Sm4In square pyramids,  an edgeedge with one S(5)Sm3In2 trigonal bipyramid,  an edgeedge with one S(4)Sm5 trigonal bipyramid,  an edgeedge with one S(6)Sm5 trigonal bipyramid, and edges with four equivalent S(1)Sm3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded to one Sm(1), two equivalent Sm(3), and one In(1) atom to form distorted SSm3In trigonal pyramids that share corners with two equivalent S(2)Sm4In square pyramids, corners with two equivalent S(5)Sm3In2 trigonal bipyramids, corners with two equivalent S(6)Sm5 trigonal bipyramids, corners with three equivalent S(1)Sm3In2 trigonal bipyramids, corners with four equivalent S(4)Sm5 trigonal bipyramids, corners with three equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(4)Sm5 trigonal bipyramid, edges with two equivalent S(5)Sm3In2 trigonal bipyramids, and  a faceface with one S(6)Sm5 trigonal bipyramid. In the sixth S site, S(4) is bonded to one Sm(2), two equivalent Sm(1), and two equivalent Sm(3) atoms to form distorted SSm5 trigonal bipyramids that share corners with four equivalent S(2)Sm4In square pyramids,  a cornercorner with one S(1)Sm3In2 trigonal bipyramid, corners with two equivalent S(6)Sm5 trigonal bipyramids, corners with four equivalent S(3)Sm3In trigonal pyramids,  an edgeedge with one S(2)Sm4In square pyramid, edges with two equivalent S(1)Sm3In2 trigonal bipyramids, edges with two equivalent S(5)Sm3In2 trigonal bipyramids, edges with two equivalent S(4)Sm5 trigonal bipyramids, edges with three equivalent S(6)Sm5 trigonal bipyramids, and  an edgeedge with one S(3)Sm3In trigonal pyramid.