Yb4SmS5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to three equivalent S(1) and three equivalent S(3) atoms to form YbS6 octahedra that share corners with three equivalent Yb(2)S6 octahedra, corners with three equivalent Sm(1)S6 octahedra, edges with three equivalent Yb(2)S6 octahedra, edges with three equivalent Sm(1)S6 octahedra, and edges with six equivalent Yb(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Yb site, Yb(2) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form a mixture of corner and edge-sharing YbS6 octahedra. The corner-sharing octahedra are not tilted. Sm(1) is bonded to six equivalent S(3) atoms to form SmS6 octahedra that share corners with six equivalent Yb(1)S6 octahedra, edges with six equivalent Yb(1)S6 octahedra, and edges with six equivalent Sm(1)S6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Yb(1) and three equivalent Yb(2) atoms to form SYb6 octahedra that share corners with three equivalent S(3)Yb3Sm3 octahedra, corners with three equivalent S(2)Yb6 octahedra, edges with three equivalent S(3)Yb3Sm3 octahedra, edges with three equivalent S(2)Yb6 octahedra, and edges with six equivalent S(1)Yb6 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded to six equivalent Yb(2) atoms to form a mixture of corner and edge-sharing SYb6 octahedra. The corner-sharing octahedra are not tilted. In the third S site, S(3) is bonded to three equivalent Yb(1) and three equivalent Sm(1) atoms to form SYb3Sm3 octahedra that share corners with three equivalent S(3)Yb3Sm3 octahedra, corners with three equivalent S(1)Yb6 octahedra, edges with three equivalent S(1)Yb6 octahedra, and edges with nine equivalent S(3)Yb3Sm3 octahedra. The corner-sharing octahedra are not tilted.
Yb4SmS5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to three equivalent S(1) and three equivalent S(3) atoms to form YbS6 octahedra that share corners with three equivalent Yb(2)S6 octahedra, corners with three equivalent Sm(1)S6 octahedra, edges with three equivalent Yb(2)S6 octahedra, edges with three equivalent Sm(1)S6 octahedra, and edges with six equivalent Yb(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. All Yb(1)-S(1) bond lengths are 2.79 Å. All Yb(1)-S(3) bond lengths are 2.79 Å. In the second Yb site, Yb(2) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form a mixture of corner and edge-sharing YbS6 octahedra. The corner-sharing octahedra are not tilted. All Yb(2)-S(1) bond lengths are 2.80 Å. All Yb(2)-S(2) bond lengths are 2.80 Å. Sm(1) is bonded to six equivalent S(3) atoms to form SmS6 octahedra that share corners with six equivalent Yb(1)S6 octahedra, edges with six equivalent Yb(1)S6 octahedra, and edges with six equivalent Sm(1)S6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Sm(1)-S(3) bond lengths are 2.84 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Yb(1) and three equivalent Yb(2) atoms to form SYb6 octahedra that share corners with three equivalent S(3)Yb3Sm3 octahedra, corners with three equivalent S(2)Yb6 octahedra, edges with three equivalent S(3)Yb3Sm3 octahedra, edges with three equivalent S(2)Yb6 octahedra, and edges with six equivalent S(1)Yb6 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded to six equivalent Yb(2) atoms to form a mixture of corner and edge-sharing SYb6 octahedra. The corner-sharing octahedra are not tilted. In the third S site, S(3) is bonded to three equivalent Yb(1) and three equivalent Sm(1) atoms to form SYb3Sm3 octahedra that share corners with three equivalent S(3)Yb3Sm3 octahedra, corners with three equivalent S(1)Yb6 octahedra, edges with three equivalent S(1)Yb6 octahedra, and edges with nine equivalent S(3)Yb3Sm3 octahedra. The corner-sharing octahedra are not tilted.