CaSm2S3 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. Ca(1) is bonded to six equivalent S(1) atoms to form CaS6 octahedra that share corners with six equivalent Sm(1)S6 octahedra, edges with six equivalent Ca(1)S6 octahedra, and edges with six equivalent Sm(1)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. Sm(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form SmS6 octahedra that share corners with three equivalent Ca(1)S6 octahedra, corners with three equivalent Sm(1)S6 octahedra, edges with three equivalent Ca(1)S6 octahedra, and edges with nine equivalent Sm(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ca(1) and three equivalent Sm(1) atoms to form SCa3Sm3 octahedra that share corners with three equivalent S(1)Ca3Sm3 octahedra, corners with three equivalent S(2)Sm6 octahedra, edges with three equivalent S(2)Sm6 octahedra, and edges with nine equivalent S(1)Ca3Sm3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second S site, S(2) is bonded to six equivalent Sm(1) atoms to form SSm6 octahedra that share corners with six equivalent S(1)Ca3Sm3 octahedra, edges with six equivalent S(1)Ca3Sm3 octahedra, and edges with six equivalent S(2)Sm6 octahedra. The corner-sharing octahedral tilt angles are 4°.
CaSm2S3 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. Ca(1) is bonded to six equivalent S(1) atoms to form CaS6 octahedra that share corners with six equivalent Sm(1)S6 octahedra, edges with six equivalent Ca(1)S6 octahedra, and edges with six equivalent Sm(1)S6 octahedra. The corner-sharing octahedral tilt angles are 2°. All Ca(1)-S(1) bond lengths are 2.83 Å. Sm(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form SmS6 octahedra that share corners with three equivalent Ca(1)S6 octahedra, corners with three equivalent Sm(1)S6 octahedra, edges with three equivalent Ca(1)S6 octahedra, and edges with nine equivalent Sm(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. All Sm(1)-S(1) bond lengths are 2.90 Å. All Sm(1)-S(2) bond lengths are 2.78 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ca(1) and three equivalent Sm(1) atoms to form SCa3Sm3 octahedra that share corners with three equivalent S(1)Ca3Sm3 octahedra, corners with three equivalent S(2)Sm6 octahedra, edges with three equivalent S(2)Sm6 octahedra, and edges with nine equivalent S(1)Ca3Sm3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second S site, S(2) is bonded to six equivalent Sm(1) atoms to form SSm6 octahedra that share corners with six equivalent S(1)Ca3Sm3 octahedra, edges with six equivalent S(1)Ca3Sm3 octahedra, and edges with six equivalent S(2)Sm6 octahedra. The corner-sharing octahedral tilt angles are 4°.