Nd2CuInS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a 8-coordinate geometry to one S(3), two equivalent S(2), two equivalent S(5), and three equivalent S(1) atoms. In the second Nd site, Nd(2) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. Cu(1) is bonded to one S(5) and three equivalent S(4) atoms to form distorted CuS4 tetrahedra that share corners with three equivalent In(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-74°. In(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form InS6 octahedra that share corners with three equivalent Cu(1)S4 tetrahedra and edges with two equivalent In(1)S6 octahedra. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Nd(1), two equivalent Nd(2), and one Cu(1) atom to form distorted SNd4Cu trigonal bipyramids that share corners with four equivalent S(4)Nd2InCu3 octahedra, corners with four equivalent S(2)Nd4In square pyramids, corners with two equivalent S(3)Nd3In2 trigonal bipyramids, corners with four equivalent S(1)Nd3In2 trigonal bipyramids, edges with two equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(1)Nd3In2 trigonal bipyramid, edges with two equivalent S(3)Nd3In2 trigonal bipyramids, edges with two equivalent S(5)Nd4Cu trigonal bipyramids, and  a faceface with one S(4)Nd2InCu3 octahedra. The corner-sharing octahedral tilt angles range from 58-65°. In the second S site, S(1) is bonded to three equivalent Nd(1) and two equivalent In(1) atoms to form SNd3In2 trigonal bipyramids that share corners with two equivalent S(4)Nd2InCu3 octahedra, corners with two equivalent S(2)Nd4In square pyramids, corners with four equivalent S(5)Nd4Cu trigonal bipyramids, corners with five equivalent S(3)Nd3In2 trigonal bipyramids, edges with three equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(3)Nd3In2 trigonal bipyramid,  an edgeedge with one S(5)Nd4Cu trigonal bipyramid, and edges with four equivalent S(1)Nd3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 85°. In the third S site, S(2) is bonded to two equivalent Nd(1), two equivalent Nd(2), and one In(1) atom to form SNd4In square pyramids that share corners with three equivalent S(4)Nd2InCu3 octahedra, corners with two equivalent S(1)Nd3In2 trigonal bipyramids, corners with four equivalent S(5)Nd4Cu trigonal bipyramids,  an edgeedge with one S(4)Nd2InCu3 octahedra, edges with two equivalent S(2)Nd4In square pyramids, edges with two equivalent S(5)Nd4Cu trigonal bipyramids, edges with three equivalent S(1)Nd3In2 trigonal bipyramids, and edges with four equivalent S(3)Nd3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-37°. In the fourth S site, S(3) is bonded to one Nd(1), two equivalent Nd(2), and two equivalent In(1) atoms to form distorted SNd3In2 trigonal bipyramids that share corners with two equivalent S(4)Nd2InCu3 octahedra, corners with two equivalent S(5)Nd4Cu trigonal bipyramids, corners with four equivalent S(3)Nd3In2 trigonal bipyramids, corners with five equivalent S(1)Nd3In2 trigonal bipyramids, edges with two equivalent S(4)Nd2InCu3 octahedra, edges with four equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(1)Nd3In2 trigonal bipyramid, and edges with two equivalent S(5)Nd4Cu trigonal bipyramids. The corner-sharing octahedral tilt angles are 46°. In the fifth S site, S(4) is bonded to two equivalent Nd(2), three equivalent Cu(1), and one In(1) atom to form distorted SNd2InCu3 octahedra that share corners with three equivalent S(2)Nd4In square pyramids, corners with two equivalent S(1)Nd3In2 trigonal bipyramids, corners with two equivalent S(3)Nd3In2 trigonal bipyramids, corners with four equivalent S(5)Nd4Cu trigonal bipyramids, edges with four equivalent S(4)Nd2InCu3 octahedra,  an edgeedge with one S(2)Nd4In square pyramid, edges with two equivalent S(3)Nd3In2 trigonal bipyramids, and  a faceface with one S(5)Nd4Cu trigonal bipyramid.
Nd2CuInS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a 8-coordinate geometry to one S(3), two equivalent S(2), two equivalent S(5), and three equivalent S(1) atoms. The Nd(1)-S(3) bond length is 3.17 Å. Both Nd(1)-S(2) bond lengths are 2.93 Å. Both Nd(1)-S(5) bond lengths are 2.88 Å. There are two shorter (2.95 Å) and one longer (3.00 Å) Nd(1)-S(1) bond length. In the second Nd site, Nd(2) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. Both Nd(2)-S(2) bond lengths are 2.90 Å. There is one shorter (3.12 Å) and one longer (3.15 Å) Nd(2)-S(3) bond length. Both Nd(2)-S(4) bond lengths are 2.94 Å. Both Nd(2)-S(5) bond lengths are 2.91 Å. Cu(1) is bonded to one S(5) and three equivalent S(4) atoms to form distorted CuS4 tetrahedra that share corners with three equivalent In(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-74°. The Cu(1)-S(5) bond length is 2.27 Å. There are two shorter (2.32 Å) and one longer (2.51 Å) Cu(1)-S(4) bond length. In(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form InS6 octahedra that share corners with three equivalent Cu(1)S4 tetrahedra and edges with two equivalent In(1)S6 octahedra. The In(1)-S(2) bond length is 2.58 Å. The In(1)-S(4) bond length is 2.61 Å. Both In(1)-S(1) bond lengths are 2.78 Å. Both In(1)-S(3) bond lengths are 2.59 Å. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Nd(1), two equivalent Nd(2), and one Cu(1) atom to form distorted SNd4Cu trigonal bipyramids that share corners with four equivalent S(4)Nd2InCu3 octahedra, corners with four equivalent S(2)Nd4In square pyramids, corners with two equivalent S(3)Nd3In2 trigonal bipyramids, corners with four equivalent S(1)Nd3In2 trigonal bipyramids, edges with two equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(1)Nd3In2 trigonal bipyramid, edges with two equivalent S(3)Nd3In2 trigonal bipyramids, edges with two equivalent S(5)Nd4Cu trigonal bipyramids, and  a faceface with one S(4)Nd2InCu3 octahedra. The corner-sharing octahedral tilt angles range from 58-65°. In the second S site, S(1) is bonded to three equivalent Nd(1) and two equivalent In(1) atoms to form SNd3In2 trigonal bipyramids that share corners with two equivalent S(4)Nd2InCu3 octahedra, corners with two equivalent S(2)Nd4In square pyramids, corners with four equivalent S(5)Nd4Cu trigonal bipyramids, corners with five equivalent S(3)Nd3In2 trigonal bipyramids, edges with three equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(3)Nd3In2 trigonal bipyramid,  an edgeedge with one S(5)Nd4Cu trigonal bipyramid, and edges with four equivalent S(1)Nd3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 85°. In the third S site, S(2) is bonded to two equivalent Nd(1), two equivalent Nd(2), and one In(1) atom to form SNd4In square pyramids that share corners with three equivalent S(4)Nd2InCu3 octahedra, corners with two equivalent S(1)Nd3In2 trigonal bipyramids, corners with four equivalent S(5)Nd4Cu trigonal bipyramids,  an edgeedge with one S(4)Nd2InCu3 octahedra, edges with two equivalent S(2)Nd4In square pyramids, edges with two equivalent S(5)Nd4Cu trigonal bipyramids, edges with three equivalent S(1)Nd3In2 trigonal bipyramids, and edges with four equivalent S(3)Nd3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-37°. In the fourth S site, S(3) is bonded to one Nd(1), two equivalent Nd(2), and two equivalent In(1) atoms to form distorted SNd3In2 trigonal bipyramids that share corners with two equivalent S(4)Nd2InCu3 octahedra, corners with two equivalent S(5)Nd4Cu trigonal bipyramids, corners with four equivalent S(3)Nd3In2 trigonal bipyramids, corners with five equivalent S(1)Nd3In2 trigonal bipyramids, edges with two equivalent S(4)Nd2InCu3 octahedra, edges with four equivalent S(2)Nd4In square pyramids,  an edgeedge with one S(1)Nd3In2 trigonal bipyramid, and edges with two equivalent S(5)Nd4Cu trigonal bipyramids. The corner-sharing octahedral tilt angles are 46°. In the fifth S site, S(4) is bonded to two equivalent Nd(2), three equivalent Cu(1), and one In(1) atom to form distorted SNd2InCu3 octahedra that share corners with three equivalent S(2)Nd4In square pyramids, corners with two equivalent S(1)Nd3In2 trigonal bipyramids, corners with two equivalent S(3)Nd3In2 trigonal bipyramids, corners with four equivalent S(5)Nd4Cu trigonal bipyramids, edges with four equivalent S(4)Nd2InCu3 octahedra,  an edgeedge with one S(2)Nd4In square pyramid, edges with two equivalent S(3)Nd3In2 trigonal bipyramids, and  a faceface with one S(5)Nd4Cu trigonal bipyramid.