Mn4FeS5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent S(1) and three equivalent S(3) atoms to form MnS6 octahedra that share corners with three equivalent Mn(2)S6 octahedra, corners with three equivalent Fe(1)S6 octahedra, edges with three equivalent Mn(2)S6 octahedra, edges with three equivalent Fe(1)S6 octahedra, and edges with six equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the second Mn site, Mn(2) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form a mixture of edge and corner-sharing MnS6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Fe(1) is bonded to six equivalent S(1) atoms to form FeS6 octahedra that share corners with six equivalent Mn(1)S6 octahedra, edges with six equivalent Mn(1)S6 octahedra, and edges with six equivalent Fe(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 Mn(1) and three equivalent Fe(1) atoms to form SMn3Fe3 octahedra that share corners with three equivalent S(1)Mn3Fe3 octahedra, corners with three equivalent S(3)Mn6 octahedra, edges with three equivalent S(3)Mn6 octahedra, and edges with nine equivalent S(1)Mn3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second S site, S(2) is bonded to six equivalent Mn(2) atoms to form a mixture of edge and corner-sharing SMn6 octahedra. The corner-sharing octahedra are not tilted. In the third S site, S(3) is bonded to three equivalent Mn(1) and three equivalent Mn(2) atoms to form SMn6 octahedra that share corners with three equivalent S(1)Mn3Fe3 octahedra, corners with three equivalent S(2)Mn6 octahedra, edges with three equivalent S(1)Mn3Fe3 octahedra, edges with three equivalent S(2)Mn6 octahedra, and edges with six equivalent S(3)Mn6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Mn4FeS5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent S(1) and three equivalent S(3) atoms to form MnS6 octahedra that share corners with three equivalent Mn(2)S6 octahedra, corners with three equivalent Fe(1)S6 octahedra, edges with three equivalent Mn(2)S6 octahedra, edges with three equivalent Fe(1)S6 octahedra, and edges with six equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Mn(1)-S(1) bond lengths are 2.52 Å. All Mn(1)-S(3) bond lengths are 2.57 Å. In the second Mn site, Mn(2) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form a mixture of edge and corner-sharing MnS6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. All Mn(2)-S(2) bond lengths are 2.53 Å. All Mn(2)-S(3) bond lengths are 2.54 Å. Fe(1) is bonded to six equivalent S(1) atoms to form FeS6 octahedra that share corners with six equivalent Mn(1)S6 octahedra, edges with six equivalent Mn(1)S6 octahedra, and edges with six equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Fe(1)-S(1) bond lengths are 2.51 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Mn(1) and three equivalent Fe(1) atoms to form SMn3Fe3 octahedra that share corners with three equivalent S(1)Mn3Fe3 octahedra, corners with three equivalent S(3)Mn6 octahedra, edges with three equivalent S(3)Mn6 octahedra, and edges with nine equivalent S(1)Mn3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second S site, S(2) is bonded to six equivalent Mn(2) atoms to form a mixture of edge and corner-sharing SMn6 octahedra. The corner-sharing octahedra are not tilted. In the third S site, S(3) is bonded to three equivalent Mn(1) and three equivalent Mn(2) atoms to form SMn6 octahedra that share corners with three equivalent S(1)Mn3Fe3 octahedra, corners with three equivalent S(2)Mn6 octahedra, edges with three equivalent S(1)Mn3Fe3 octahedra, edges with three equivalent S(2)Mn6 octahedra, and edges with six equivalent S(3)Mn6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.