Nd4NiS7 crystallizes in the hexagonal P6_3 space group. There are two inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a distorted rectangular see-saw-like geometry to one S(2) and three equivalent S(1) atoms. In the second Nd site, Nd(2) is bonded in a 7-coordinate geometry to one S(2), three equivalent S(1), and three equivalent S(3) atoms. Ni(1) is bonded to six equivalent S(3) atoms to form distorted face-sharing NiS6 octahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Nd(1) and three equivalent Nd(2) atoms. In the second S site, S(2) is bonded to one Nd(1) and three equivalent Nd(2) atoms to form corner-sharing SNd4 tetrahedra. In the third S site, S(3) is bonded to three equivalent Nd(2) and two equivalent Ni(1) atoms to form distorted SNd3Ni2 square pyramids that share corners with two equivalent S(3)Nd3Ni2 square pyramids, corners with three equivalent S(2)Nd4 tetrahedra, edges with four equivalent S(3)Nd3Ni2 square pyramids, and faces with two equivalent S(3)Nd3Ni2 square pyramids.
Nd4NiS7 crystallizes in the hexagonal P6_3 space group. There are two inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a distorted rectangular see-saw-like geometry to one S(2) and three equivalent S(1) atoms. The Nd(1)-S(2) bond length is 2.65 Å. All Nd(1)-S(1) bond lengths are 2.67 Å. In the second Nd site, Nd(2) is bonded in a 7-coordinate geometry to one S(2), three equivalent S(1), and three equivalent S(3) atoms. The Nd(2)-S(2) bond length is 2.74 Å. There are a spread of Nd(2)-S(1) bond distances ranging from 2.88-3.18 Å. There are a spread of Nd(2)-S(3) bond distances ranging from 2.84-2.96 Å. Ni(1) is bonded to six equivalent S(3) atoms to form distorted face-sharing NiS6 octahedra. There are three shorter (2.40 Å) and three longer (2.72 Å) Ni(1)-S(3) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Nd(1) and three equivalent Nd(2) atoms. In the second S site, S(2) is bonded to one Nd(1) and three equivalent Nd(2) atoms to form corner-sharing SNd4 tetrahedra. In the third S site, S(3) is bonded to three equivalent Nd(2) and two equivalent Ni(1) atoms to form distorted SNd3Ni2 square pyramids that share corners with two equivalent S(3)Nd3Ni2 square pyramids, corners with three equivalent S(2)Nd4 tetrahedra, edges with four equivalent S(3)Nd3Ni2 square pyramids, and faces with two equivalent S(3)Nd3Ni2 square pyramids.