Ta4MnS8 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Ta sites. In the first Ta site, Ta(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share corners with four equivalent Mn(1)S6 octahedra, edges with two equivalent Ta(2)S6 pentagonal pyramids, and edges with four equivalent Ta(1)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. In the second Ta site, Ta(2) is bonded to six equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share edges with six equivalent Ta(1)S6 pentagonal pyramids and faces with two equivalent Mn(1)S6 octahedra. Mn(1) is bonded to six equivalent S(1) atoms to form MnS6 octahedra that share corners with twelve equivalent Ta(1)S6 pentagonal pyramids and faces with two equivalent Ta(2)S6 pentagonal pyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ta(2), two equivalent Ta(1), and one Mn(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent Ta(1) atoms.
Ta4MnS8 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Ta sites. In the first Ta site, Ta(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share corners with four equivalent Mn(1)S6 octahedra, edges with two equivalent Ta(2)S6 pentagonal pyramids, and edges with four equivalent Ta(1)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. Both Ta(1)-S(2) bond lengths are 2.45 Å. All Ta(1)-S(1) bond lengths are 2.49 Å. In the second Ta site, Ta(2) is bonded to six equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share edges with six equivalent Ta(1)S6 pentagonal pyramids and faces with two equivalent Mn(1)S6 octahedra. All Ta(2)-S(1) bond lengths are 2.49 Å. Mn(1) is bonded to six equivalent S(1) atoms to form MnS6 octahedra that share corners with twelve equivalent Ta(1)S6 pentagonal pyramids and faces with two equivalent Ta(2)S6 pentagonal pyramids. All Mn(1)-S(1) bond lengths are 2.52 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ta(2), two equivalent Ta(1), and one Mn(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent Ta(1) atoms.