Mn(NbS2)4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form distorted NbS6 pentagonal pyramids that share corners with four equivalent Mn(1)S6 octahedra, edges with two equivalent Nb(2)S6 pentagonal pyramids, and edges with four equivalent Nb(1)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. In the second Nb site, Nb(2) is bonded to six equivalent S(2) atoms to form distorted NbS6 pentagonal pyramids that share edges with six equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Mn(1)S6 octahedra. Mn(1) is bonded to six equivalent S(2) atoms to form MnS6 octahedra that share corners with twelve equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Nb(2)S6 pentagonal pyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to three equivalent Nb(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Nb(2), two equivalent Nb(1), and one Mn(1) atom.
Mn(NbS2)4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form distorted NbS6 pentagonal pyramids that share corners with four equivalent Mn(1)S6 octahedra, edges with two equivalent Nb(2)S6 pentagonal pyramids, and edges with four equivalent Nb(1)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. Both Nb(1)-S(1) bond lengths are 2.46 Å. All Nb(1)-S(2) bond lengths are 2.52 Å. In the second Nb site, Nb(2) is bonded to six equivalent S(2) atoms to form distorted NbS6 pentagonal pyramids that share edges with six equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Mn(1)S6 octahedra. All Nb(2)-S(2) bond lengths are 2.50 Å. Mn(1) is bonded to six equivalent S(2) atoms to form MnS6 octahedra that share corners with twelve equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Nb(2)S6 pentagonal pyramids. All Mn(1)-S(2) bond lengths are 2.51 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to three equivalent Nb(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Nb(2), two equivalent Nb(1), and one Mn(1) atom.