Na6MnS4 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one S(2) and four equivalent S(1) atoms. In the second Na site, Na(2) is bonded to one S(2) and three equivalent S(1) atoms to form distorted NaS4 tetrahedra that share corners with two equivalent Mn(1)S4 tetrahedra, corners with eight equivalent Na(2)S4 tetrahedra, and  an edgeedge with one Mn(1)S4 tetrahedra. Mn(1) is bonded to one S(2) and three equivalent S(1) atoms to form MnS4 tetrahedra that share corners with six equivalent Na(2)S4 tetrahedra and edges with three equivalent Na(2)S4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to three equivalent Na(2), four equivalent Na(1), and one Mn(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and one Mn(1) atom.
Na6MnS4 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one S(2) and four equivalent S(1) atoms. The Na(1)-S(2) bond length is 2.79 Å. There are two shorter (2.90 Å) and two longer (3.18 Å) Na(1)-S(1) bond lengths. In the second Na site, Na(2) is bonded to one S(2) and three equivalent S(1) atoms to form distorted NaS4 tetrahedra that share corners with two equivalent Mn(1)S4 tetrahedra, corners with eight equivalent Na(2)S4 tetrahedra, and  an edgeedge with one Mn(1)S4 tetrahedra. The Na(2)-S(2) bond length is 2.92 Å. There are two shorter (2.73 Å) and one longer (2.80 Å) Na(2)-S(1) bond length. Mn(1) is bonded to one S(2) and three equivalent S(1) atoms to form MnS4 tetrahedra that share corners with six equivalent Na(2)S4 tetrahedra and edges with three equivalent Na(2)S4 tetrahedra. The Mn(1)-S(2) bond length is 2.41 Å. All Mn(1)-S(1) bond lengths are 2.40 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to three equivalent Na(2), four equivalent Na(1), and one Mn(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and one Mn(1) atom.