La3MnS5 crystallizes in the hexagonal P6_3/mcm space group. La(1) is bonded in a 7-coordinate geometry to three equivalent S(1) and four equivalent S(2) atoms. Mn(1) is bonded to six equivalent S(1) atoms to form face-sharing MnS6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent La(1) and two equivalent Mn(1) atoms to form distorted SLa3Mn2 trigonal bipyramids that share corners with four equivalent S(2)La6 octahedra, corners with ten equivalent S(1)La3Mn2 trigonal bipyramids, edges with four equivalent S(2)La6 octahedra, and faces with two equivalent S(1)La3Mn2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 47°. In the second S site, S(2) is bonded to six equivalent La(1) atoms to form SLa6 octahedra that share corners with six equivalent S(2)La6 octahedra, corners with six equivalent S(1)La3Mn2 trigonal bipyramids, edges with three equivalent S(2)La6 octahedra, edges with six equivalent S(1)La3Mn2 trigonal bipyramids, and faces with two equivalent S(2)La6 octahedra. The corner-sharing octahedral tilt angles are 32°.
La3MnS5 crystallizes in the hexagonal P6_3/mcm space group. La(1) is bonded in a 7-coordinate geometry to three equivalent S(1) and four equivalent S(2) atoms. There are two shorter (2.83 Å) and one longer (2.95 Å) La(1)-S(1) bond length. All La(1)-S(2) bond lengths are 3.04 Å. Mn(1) is bonded to six equivalent S(1) atoms to form face-sharing MnS6 octahedra. All Mn(1)-S(1) bond lengths are 2.62 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent La(1) and two equivalent Mn(1) atoms to form distorted SLa3Mn2 trigonal bipyramids that share corners with four equivalent S(2)La6 octahedra, corners with ten equivalent S(1)La3Mn2 trigonal bipyramids, edges with four equivalent S(2)La6 octahedra, and faces with two equivalent S(1)La3Mn2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 47°. In the second S site, S(2) is bonded to six equivalent La(1) atoms to form SLa6 octahedra that share corners with six equivalent S(2)La6 octahedra, corners with six equivalent S(1)La3Mn2 trigonal bipyramids, edges with three equivalent S(2)La6 octahedra, edges with six equivalent S(1)La3Mn2 trigonal bipyramids, and faces with two equivalent S(2)La6 octahedra. The corner-sharing octahedral tilt angles are 32°.