Na6Mn(SO4)4 is Esseneite-like structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(6), one O(8), two equivalent O(3), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded to one O(2), one O(4), one O(7), one O(8), and two equivalent O(6) atoms to form NaO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra,  an edgeedge with one Na(2)O6 octahedra, and  an edgeedge with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(3), one O(5), one O(7), one O(8), two equivalent O(1), and two equivalent O(2) atoms. Mn(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent S(2)O4 tetrahedra, and corners with four equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form SO4 tetrahedra that share corners with two equivalent Na(2)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-60°. In the second S site, S(2) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, and  an edgeedge with one Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-45°. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one S(1) atom. In the second O site, O(5) is bonded in a 3-coordinate geometry to one Na(3), one Mn(1), and one S(1) atom. In the third O site, O(6) is bonded in a distorted see-saw-like geometry to one Na(1), two equivalent Na(2), and one S(2) atom. In the fourth O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one S(2) atom. In the fifth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one S(2) atom. In the sixth O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(3), one Mn(1), and one S(1) atom. In the seventh O site, O(2) is bonded to one Na(2), two equivalent Na(3), and one S(1) atom to form distorted edge-sharing ONa3S trigonal pyramids. In the eighth O site, O(3) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(1), and one S(2) atom.
Na6Mn(SO4)4 is Esseneite-like structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(6), one O(8), two equivalent O(3), and two equivalent O(4) atoms. The Na(1)-O(6) bond length is 2.38 Å. The Na(1)-O(8) bond length is 2.45 Å. There is one shorter (2.33 Å) and one longer (2.40 Å) Na(1)-O(3) bond length. There is one shorter (2.40 Å) and one longer (2.74 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded to one O(2), one O(4), one O(7), one O(8), and two equivalent O(6) atoms to form NaO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra,  an edgeedge with one Na(2)O6 octahedra, and  an edgeedge with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. The Na(2)-O(2) bond length is 2.32 Å. The Na(2)-O(4) bond length is 2.44 Å. The Na(2)-O(7) bond length is 2.41 Å. The Na(2)-O(8) bond length is 2.33 Å. There is one shorter (2.27 Å) and one longer (2.42 Å) Na(2)-O(6) bond length. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(3), one O(5), one O(7), one O(8), two equivalent O(1), and two equivalent O(2) atoms. The Na(3)-O(3) bond length is 2.85 Å. The Na(3)-O(5) bond length is 2.53 Å. The Na(3)-O(7) bond length is 2.55 Å. The Na(3)-O(8) bond length is 2.34 Å. There is one shorter (2.29 Å) and one longer (2.98 Å) Na(3)-O(1) bond length. There is one shorter (2.45 Å) and one longer (2.49 Å) Na(3)-O(2) bond length. Mn(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent S(2)O4 tetrahedra, and corners with four equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. Both Mn(1)-O(1) bond lengths are 2.15 Å. Both Mn(1)-O(5) bond lengths are 2.18 Å. Both Mn(1)-O(7) bond lengths are 2.16 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form SO4 tetrahedra that share corners with two equivalent Na(2)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-60°. The S(1)-O(1) bond length is 1.49 Å. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(4) bond length is 1.47 Å. The S(1)-O(5) bond length is 1.48 Å. In the second S site, S(2) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, and  an edgeedge with one Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-45°. The S(2)-O(3) bond length is 1.46 Å. The S(2)-O(6) bond length is 1.48 Å. The S(2)-O(7) bond length is 1.50 Å. The S(2)-O(8) bond length is 1.47 Å. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one S(1) atom. In the second O site, O(5) is bonded in a 3-coordinate geometry to one Na(3), one Mn(1), and one S(1) atom. In the third O site, O(6) is bonded in a distorted see-saw-like geometry to one Na(1), two equivalent Na(2), and one S(2) atom. In the fourth O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one S(2) atom. In the fifth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one S(2) atom. In the sixth O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(3), one Mn(1), and one S(1) atom. In the seventh O site, O(2) is bonded to one Na(2), two equivalent Na(3), and one S(1) atom to form distorted edge-sharing ONa3S trigonal pyramids. In the eighth O site, O(3) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(1), and one S(2) atom.