SmBiS3 crystallizes in the orthorhombic Pnma space group. Sm(1) is bonded to two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms to form a mixture of distorted corner and edge-sharing SmS7 pentagonal bipyramids. Bi(1) is bonded in a 5-coordinate geometry to two equivalent S(3) and three equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Sm(1) and three equivalent Bi(1) atoms to form distorted SSm2Bi3 square pyramids that share corners with four equivalent S(3)Sm2Bi2 trigonal pyramids, edges with four equivalent S(1)Sm2Bi3 square pyramids, and edges with three equivalent S(3)Sm2Bi2 trigonal pyramids. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent Sm(1) atoms. In the third S site, S(3) is bonded to two equivalent Sm(1) and two equivalent Bi(1) atoms to form SSm2Bi2 trigonal pyramids that share corners with four equivalent S(1)Sm2Bi3 square pyramids, corners with four equivalent S(3)Sm2Bi2 trigonal pyramids, and edges with three equivalent S(1)Sm2Bi3 square pyramids.
SmBiS3 crystallizes in the orthorhombic Pnma space group. Sm(1) is bonded to two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms to form a mixture of distorted corner and edge-sharing SmS7 pentagonal bipyramids. Both Sm(1)-S(1) bond lengths are 2.95 Å. There is one shorter (2.95 Å) and one longer (2.96 Å) Sm(1)-S(3) bond length. There are two shorter (2.73 Å) and one longer (2.80 Å) Sm(1)-S(2) bond length. Bi(1) is bonded in a 5-coordinate geometry to two equivalent S(3) and three equivalent S(1) atoms. Both Bi(1)-S(3) bond lengths are 2.74 Å. There is one shorter (2.65 Å) and two longer (3.06 Å) Bi(1)-S(1) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Sm(1) and three equivalent Bi(1) atoms to form distorted SSm2Bi3 square pyramids that share corners with four equivalent S(3)Sm2Bi2 trigonal pyramids, edges with four equivalent S(1)Sm2Bi3 square pyramids, and edges with three equivalent S(3)Sm2Bi2 trigonal pyramids. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent Sm(1) atoms. In the third S site, S(3) is bonded to two equivalent Sm(1) and two equivalent Bi(1) atoms to form SSm2Bi2 trigonal pyramids that share corners with four equivalent S(1)Sm2Bi3 square pyramids, corners with four equivalent S(3)Sm2Bi2 trigonal pyramids, and edges with three equivalent S(1)Sm2Bi3 square pyramids.