BaSm2FeS5 crystallizes in the tetragonal I4/mcm space group. Ba(1) is bonded in a 10-coordinate geometry to two equivalent S(2) and eight equivalent S(1) atoms. Sm(1) is bonded in a 8-coordinate geometry to two equivalent S(2) and six equivalent S(1) atoms. Fe(1) is bonded in a distorted tetrahedral geometry to four equivalent S(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), three equivalent Sm(1), and one Fe(1) atom to form distorted SBa2Sm3Fe octahedra that share corners with four equivalent S(2)Ba2Sm4 octahedra, corners with ten equivalent S(1)Ba2Sm3Fe octahedra, edges with eight equivalent S(1)Ba2Sm3Fe octahedra, faces with two equivalent S(1)Ba2Sm3Fe octahedra, and faces with two equivalent S(2)Ba2Sm4 octahedra. The corner-sharing octahedral tilt angles range from 33-62°. In the second S site, S(2) is bonded to two equivalent Ba(1) and four equivalent Sm(1) atoms to form SBa2Sm4 octahedra that share corners with six equivalent S(2)Ba2Sm4 octahedra, corners with sixteen equivalent S(1)Ba2Sm3Fe octahedra, and faces with eight equivalent S(1)Ba2Sm3Fe octahedra. The corner-sharing octahedral tilt angles range from 0-62°.
BaSm2FeS5 crystallizes in the tetragonal I4/mcm space group. Ba(1) is bonded in a 10-coordinate geometry to two equivalent S(2) and eight equivalent S(1) atoms. Both Ba(1)-S(2) bond lengths are 3.37 Å. All Ba(1)-S(1) bond lengths are 3.37 Å. Sm(1) is bonded in a 8-coordinate geometry to two equivalent S(2) and six equivalent S(1) atoms. Both Sm(1)-S(2) bond lengths are 2.93 Å. There are two shorter (2.77 Å) and four longer (3.02 Å) Sm(1)-S(1) bond lengths. Fe(1) is bonded in a distorted tetrahedral geometry to four equivalent S(1) atoms. All Fe(1)-S(1) bond lengths are 2.26 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), three equivalent Sm(1), and one Fe(1) atom to form distorted SBa2Sm3Fe octahedra that share corners with four equivalent S(2)Ba2Sm4 octahedra, corners with ten equivalent S(1)Ba2Sm3Fe octahedra, edges with eight equivalent S(1)Ba2Sm3Fe octahedra, faces with two equivalent S(1)Ba2Sm3Fe octahedra, and faces with two equivalent S(2)Ba2Sm4 octahedra. The corner-sharing octahedral tilt angles range from 33-62°. In the second S site, S(2) is bonded to two equivalent Ba(1) and four equivalent Sm(1) atoms to form SBa2Sm4 octahedra that share corners with six equivalent S(2)Ba2Sm4 octahedra, corners with sixteen equivalent S(1)Ba2Sm3Fe octahedra, and faces with eight equivalent S(1)Ba2Sm3Fe octahedra. The corner-sharing octahedral tilt angles range from 0-62°.