Nd3InS6 crystallizes in the orthorhombic P2_12_12 space group. There are three inequivalent Nd sites. In the first Nd site, Nd(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 Nd site, Nd(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 Nd site, Nd(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 NdS7 pentagonal bipyramids that share  a cornercorner with one In(2)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent Nd(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 Nd(3)S7 pentagonal bipyramids. In the second In site, In(2) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form distorted InS4 tetrahedra that share corners with two equivalent Nd(3)S7 pentagonal bipyramids. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Nd(2), two equivalent Nd(1), and two equivalent Nd(3) atoms to form distorted SNd5 trigonal bipyramids that share corners with four equivalent S(2)Nd4In square pyramids,  a cornercorner with one S(6)Nd3In2 trigonal bipyramid, corners with two equivalent S(4)Nd5 trigonal bipyramids, corners with four equivalent S(3)Nd3In trigonal pyramids,  an edgeedge with one S(2)Nd4In square pyramid, edges with two equivalent S(6)Nd3In2 trigonal bipyramids, edges with two equivalent S(5)Nd5 trigonal bipyramids, edges with three equivalent S(4)Nd5 trigonal bipyramids, and  an edgeedge with one S(3)Nd3In trigonal pyramid. In the second S site, S(6) is bonded to one Nd(1), one Nd(2), one Nd(3), and two equivalent In(1) atoms to form SNd3In2 trigonal bipyramids that share  a cornercorner with one S(4)Nd5 trigonal bipyramid,  a cornercorner with one S(5)Nd5 trigonal bipyramid, corners with four equivalent S(6)Nd3In2 trigonal bipyramids, corners with three equivalent S(3)Nd3In trigonal pyramids, edges with four equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(6)Nd3In2 trigonal bipyramid, edges with two equivalent S(4)Nd5 trigonal bipyramids, and edges with two equivalent S(5)Nd5 trigonal bipyramids. In the third S site, S(1) is bonded in a distorted see-saw-like geometry to one Nd(1), two equivalent Nd(2), and one In(2) atom. In the fourth S site, S(2) is bonded to two equivalent Nd(2), two equivalent Nd(3), and one In(1) atom to form SNd4In square pyramids that share  a cornercorner with one S(2)Nd4In square pyramid, corners with four equivalent S(4)Nd5 trigonal bipyramids, corners with four equivalent S(5)Nd5 trigonal bipyramids, corners with two equivalent S(3)Nd3In trigonal pyramids, edges with two equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(4)Nd5 trigonal bipyramid,  an edgeedge with one S(5)Nd5 trigonal bipyramid, and edges with four equivalent S(6)Nd3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded to one Nd(3), two equivalent Nd(1), and one In(2) atom to form SNd3In trigonal pyramids that share corners with two equivalent S(2)Nd4In square pyramids, corners with two equivalent S(4)Nd5 trigonal bipyramids, corners with three equivalent S(6)Nd3In2 trigonal bipyramids, corners with four equivalent S(5)Nd5 trigonal bipyramids, corners with three equivalent S(3)Nd3In trigonal pyramids,  an edgeedge with one S(5)Nd5 trigonal bipyramid, and  a faceface with one S(4)Nd5 trigonal bipyramid. In the sixth S site, S(4) is bonded to one Nd(3), two equivalent Nd(1), and two equivalent Nd(2) atoms to form distorted SNd5 trigonal bipyramids that share corners with four equivalent S(2)Nd4In square pyramids,  a cornercorner with one S(6)Nd3In2 trigonal bipyramid, corners with two equivalent S(5)Nd5 trigonal bipyramids, corners with two equivalent S(3)Nd3In trigonal pyramids,  an edgeedge with one S(2)Nd4In square pyramid, edges with two equivalent S(6)Nd3In2 trigonal bipyramids, edges with two equivalent S(4)Nd5 trigonal bipyramids, edges with three equivalent S(5)Nd5 trigonal bipyramids, and  a faceface with one S(3)Nd3In trigonal pyramid.
Nd3InS6 crystallizes in the orthorhombic P2_12_12 space group. There are three inequivalent Nd sites. In the first Nd site, Nd(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 Nd(1)-S(1) bond length is 2.94 Å. The Nd(1)-S(6) bond length is 2.96 Å. Both Nd(1)-S(3) bond lengths are 2.91 Å. There is one shorter (2.97 Å) and one longer (2.99 Å) Nd(1)-S(4) bond length. There is one shorter (2.94 Å) and one longer (2.95 Å) Nd(1)-S(5) bond length. In the second Nd site, Nd(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 Nd(2)-S(5) bond length is 3.12 Å. The Nd(2)-S(6) bond length is 3.15 Å. There is one shorter (2.89 Å) and one longer (2.91 Å) Nd(2)-S(1) bond length. There is one shorter (3.03 Å) and one longer (3.05 Å) Nd(2)-S(2) bond length. There is one shorter (2.87 Å) and one longer (2.88 Å) Nd(2)-S(4) bond length. In the third Nd site, Nd(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 NdS7 pentagonal bipyramids that share  a cornercorner with one In(2)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent Nd(3)S7 pentagonal bipyramids. The Nd(3)-S(3) bond length is 2.84 Å. The Nd(3)-S(4) bond length is 2.96 Å. The Nd(3)-S(6) bond length is 3.01 Å. There is one shorter (2.90 Å) and one longer (2.91 Å) Nd(3)-S(2) bond length. Both Nd(3)-S(5) bond lengths are 2.83 Å. 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 Nd(3)S7 pentagonal bipyramids. Both In(1)-S(2) bond lengths are 2.62 Å. All In(1)-S(6) bond lengths are 2.65 Å. In the second In site, In(2) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form distorted InS4 tetrahedra that share corners with two equivalent Nd(3)S7 pentagonal bipyramids. Both In(2)-S(1) bond lengths are 2.51 Å. Both In(2)-S(3) bond lengths are 2.45 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded to one Nd(2), two equivalent Nd(1), and two equivalent Nd(3) atoms to form distorted SNd5 trigonal bipyramids that share corners with four equivalent S(2)Nd4In square pyramids,  a cornercorner with one S(6)Nd3In2 trigonal bipyramid, corners with two equivalent S(4)Nd5 trigonal bipyramids, corners with four equivalent S(3)Nd3In trigonal pyramids,  an edgeedge with one S(2)Nd4In square pyramid, edges with two equivalent S(6)Nd3In2 trigonal bipyramids, edges with two equivalent S(5)Nd5 trigonal bipyramids, edges with three equivalent S(4)Nd5 trigonal bipyramids, and  an edgeedge with one S(3)Nd3In trigonal pyramid. In the second S site, S(6) is bonded to one Nd(1), one Nd(2), one Nd(3), and two equivalent In(1) atoms to form SNd3In2 trigonal bipyramids that share  a cornercorner with one S(4)Nd5 trigonal bipyramid,  a cornercorner with one S(5)Nd5 trigonal bipyramid, corners with four equivalent S(6)Nd3In2 trigonal bipyramids, corners with three equivalent S(3)Nd3In trigonal pyramids, edges with four equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(6)Nd3In2 trigonal bipyramid, edges with two equivalent S(4)Nd5 trigonal bipyramids, and edges with two equivalent S(5)Nd5 trigonal bipyramids. In the third S site, S(1) is bonded in a distorted see-saw-like geometry to one Nd(1), two equivalent Nd(2), and one In(2) atom. In the fourth S site, S(2) is bonded to two equivalent Nd(2), two equivalent Nd(3), and one In(1) atom to form SNd4In square pyramids that share  a cornercorner with one S(2)Nd4In square pyramid, corners with four equivalent S(4)Nd5 trigonal bipyramids, corners with four equivalent S(5)Nd5 trigonal bipyramids, corners with two equivalent S(3)Nd3In trigonal pyramids, edges with two equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(4)Nd5 trigonal bipyramid,  an edgeedge with one S(5)Nd5 trigonal bipyramid, and edges with four equivalent S(6)Nd3In2 trigonal bipyramids. In the fifth S site, S(3) is bonded to one Nd(3), two equivalent Nd(1), and one In(2) atom to form SNd3In trigonal pyramids that share corners with two equivalent S(2)Nd4In square pyramids, corners with two equivalent S(4)Nd5 trigonal bipyramids, corners with three equivalent S(6)Nd3In2 trigonal bipyramids, corners with four equivalent S(5)Nd5 trigonal bipyramids, corners with three equivalent S(3)Nd3In trigonal pyramids,  an edgeedge with one S(5)Nd5 trigonal bipyramid, and  a faceface with one S(4)Nd5 trigonal bipyramid. In the sixth S site, S(4) is bonded to one Nd(3), two equivalent Nd(1), and two equivalent Nd(2) atoms to form distorted SNd5 trigonal bipyramids that share corners with four equivalent S(2)Nd4In square pyramids,  a cornercorner with one S(6)Nd3In2 trigonal bipyramid, corners with two equivalent S(5)Nd5 trigonal bipyramids, corners with two equivalent S(3)Nd3In trigonal pyramids,  an edgeedge with one S(2)Nd4In square pyramid, edges with two equivalent S(6)Nd3In2 trigonal bipyramids, edges with two equivalent S(4)Nd5 trigonal bipyramids, edges with three equivalent S(5)Nd5 trigonal bipyramids, and  a faceface with one S(3)Nd3In trigonal pyramid.