Na2Mn2S3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted rectangular see-saw-like geometry to one S(2) and three equivalent S(1) atoms. In the second Na site, Na(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted NaS6 octahedra that share corners with four equivalent Mn(1)S4 tetrahedra, corners with four equivalent Mn(2)S4 tetrahedra, edges with three equivalent Na(3)S6 octahedra, edges with two equivalent Mn(1)S4 tetrahedra, and edges with two equivalent Mn(2)S4 tetrahedra. In the third Na site, Na(3) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form NaS6 octahedra that share corners with two equivalent Mn(2)S4 tetrahedra, corners with four equivalent Mn(1)S4 tetrahedra, edges with two equivalent Na(3)S6 octahedra, edges with three equivalent Na(2)S6 octahedra, edges with two equivalent Mn(1)S4 tetrahedra, and edges with four equivalent Mn(2)S4 tetrahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted MnS4 tetrahedra that share corners with two equivalent Na(2)S6 octahedra, corners with two equivalent Na(3)S6 octahedra, corners with three equivalent Mn(2)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra,  an edgeedge with one Na(3)S6 octahedra,  an edgeedge with one Mn(1)S4 tetrahedra, and  an edgeedge with one Mn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-55°. In the second Mn site, Mn(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form MnS4 tetrahedra that share  a cornercorner with one Na(3)S6 octahedra, corners with two equivalent Na(2)S6 octahedra, corners with two equivalent Mn(2)S4 tetrahedra, corners with three equivalent Mn(1)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, edges with two equivalent Na(3)S6 octahedra, and  an edgeedge with one Mn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-50°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Na(2), three equivalent Na(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner, face, and edge-sharing SNa4Mn2 pentagonal pyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mn(2), and two equivalent Mn(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Na(2), two equivalent Na(3), one Mn(1), and two equivalent Mn(2) atoms.
Na2Mn2S3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted rectangular see-saw-like geometry to one S(2) and three equivalent S(1) atoms. The Na(1)-S(2) bond length is 2.76 Å. There are a spread of Na(1)-S(1) bond distances ranging from 2.76-2.84 Å. In the second Na site, Na(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted NaS6 octahedra that share corners with four equivalent Mn(1)S4 tetrahedra, corners with four equivalent Mn(2)S4 tetrahedra, edges with three equivalent Na(3)S6 octahedra, edges with two equivalent Mn(1)S4 tetrahedra, and edges with two equivalent Mn(2)S4 tetrahedra. Both Na(2)-S(1) bond lengths are 2.99 Å. Both Na(2)-S(2) bond lengths are 2.91 Å. Both Na(2)-S(3) bond lengths are 2.95 Å. In the third Na site, Na(3) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form NaS6 octahedra that share corners with two equivalent Mn(2)S4 tetrahedra, corners with four equivalent Mn(1)S4 tetrahedra, edges with two equivalent Na(3)S6 octahedra, edges with three equivalent Na(2)S6 octahedra, edges with two equivalent Mn(1)S4 tetrahedra, and edges with four equivalent Mn(2)S4 tetrahedra. Both Na(3)-S(2) bond lengths are 2.92 Å. There are two shorter (2.94 Å) and two longer (2.98 Å) Na(3)-S(3) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted MnS4 tetrahedra that share corners with two equivalent Na(2)S6 octahedra, corners with two equivalent Na(3)S6 octahedra, corners with three equivalent Mn(2)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra,  an edgeedge with one Na(3)S6 octahedra,  an edgeedge with one Mn(1)S4 tetrahedra, and  an edgeedge with one Mn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-55°. The Mn(1)-S(1) bond length is 2.40 Å. The Mn(1)-S(3) bond length is 2.45 Å. There is one shorter (2.45 Å) and one longer (2.49 Å) Mn(1)-S(2) bond length. In the second Mn site, Mn(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form MnS4 tetrahedra that share  a cornercorner with one Na(3)S6 octahedra, corners with two equivalent Na(2)S6 octahedra, corners with two equivalent Mn(2)S4 tetrahedra, corners with three equivalent Mn(1)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, edges with two equivalent Na(3)S6 octahedra, and  an edgeedge with one Mn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-50°. The Mn(2)-S(1) bond length is 2.40 Å. The Mn(2)-S(2) bond length is 2.46 Å. Both Mn(2)-S(3) bond lengths are 2.46 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Na(2), three equivalent Na(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner, face, and edge-sharing SNa4Mn2 pentagonal pyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mn(2), and two equivalent Mn(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Na(2), two equivalent Na(3), one Mn(1), and two equivalent Mn(2) atoms.