Sm4NiS7 crystallizes in the hexagonal P6_3 space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a distorted trigonal pyramidal geometry to one S(2) and three equivalent S(1) atoms. In the second Sm site, Sm(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 rectangular see-saw-like geometry to one Sm(1) and three equivalent Sm(2) atoms. In the second S site, S(2) is bonded to one Sm(1) and three equivalent Sm(2) atoms to form corner-sharing SSm4 tetrahedra. In the third S site, S(3) is bonded to three equivalent Sm(2) and two equivalent Ni(1) atoms to form distorted SSm3Ni2 square pyramids that share corners with two equivalent S(3)Sm3Ni2 square pyramids, corners with three equivalent S(2)Sm4 tetrahedra, edges with four equivalent S(3)Sm3Ni2 square pyramids, and faces with two equivalent S(3)Sm3Ni2 square pyramids.
Sm4NiS7 crystallizes in the hexagonal P6_3 space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a distorted trigonal pyramidal geometry to one S(2) and three equivalent S(1) atoms. The Sm(1)-S(2) bond length is 2.61 Å. All Sm(1)-S(1) bond lengths are 2.64 Å. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one S(2), three equivalent S(1), and three equivalent S(3) atoms. The Sm(2)-S(2) bond length is 2.71 Å. There are a spread of Sm(2)-S(1) bond distances ranging from 2.86-2.99 Å. There are a spread of Sm(2)-S(3) bond distances ranging from 2.79-3.07 Å. Ni(1) is bonded to six equivalent S(3) atoms to form distorted face-sharing NiS6 octahedra. There are three shorter (2.43 Å) and three longer (2.65 Å) Ni(1)-S(3) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Sm(1) and three equivalent Sm(2) atoms. In the second S site, S(2) is bonded to one Sm(1) and three equivalent Sm(2) atoms to form corner-sharing SSm4 tetrahedra. In the third S site, S(3) is bonded to three equivalent Sm(2) and two equivalent Ni(1) atoms to form distorted SSm3Ni2 square pyramids that share corners with two equivalent S(3)Sm3Ni2 square pyramids, corners with three equivalent S(2)Sm4 tetrahedra, edges with four equivalent S(3)Sm3Ni2 square pyramids, and faces with two equivalent S(3)Sm3Ni2 square pyramids.