Na5Mn3S4(O4F)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(6), two equivalent O(8), and two equivalent F(2) atoms to form distorted NaO4F2 octahedra that share corners with two equivalent Mn(2)O5F octahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 68°. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), two equivalent O(8), one F(2), and two equivalent F(1) atoms. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), two equivalent O(7), and one F(1) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(6), two equivalent F(1), and two equivalent F(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(2)O5F octahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Na(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one F(2) atom to form MnO5F octahedra that share  a cornercorner with one Na(1)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent S(2)O4 tetrahedra, and corners with three equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-68°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O4F2 octahedra and corners with three equivalent Mn(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 36-58°. In the second S site, S(2) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, and corners with two equivalent Mn(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 23-59°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one S(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(2), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(3), one Mn(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(2) and one S(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one S(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to two equivalent Na(3), one Mn(2), and one S(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one S(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Na(3), two equivalent Na(2), and one Mn(1) atom to form distorted FNa3Mn trigonal pyramids that share corners with two equivalent F(2)Na2Mn2 tetrahedra,  a cornercorner with one F(1)Na3Mn trigonal pyramid,  an edgeedge with one F(2)Na2Mn2 tetrahedra, and  an edgeedge with one F(1)Na3Mn trigonal pyramid. In the second F site, F(2) is bonded to one Na(1), one Na(2), one Mn(1), and one Mn(2) atom to form FNa2Mn2 tetrahedra that share corners with two equivalent F(2)Na2Mn2 tetrahedra, corners with two equivalent F(1)Na3Mn trigonal pyramids, and  an edgeedge with one F(1)Na3Mn trigonal pyramid.
Na5Mn3S4(O4F)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(6), two equivalent O(8), and two equivalent F(2) atoms to form distorted NaO4F2 octahedra that share corners with two equivalent Mn(2)O5F octahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 68°. Both Na(1)-O(6) bond lengths are 2.48 Å. Both Na(1)-O(8) bond lengths are 2.47 Å. Both Na(1)-F(2) bond lengths are 2.30 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), two equivalent O(8), one F(2), and two equivalent F(1) atoms. The Na(2)-O(1) bond length is 2.44 Å. The Na(2)-O(2) bond length is 2.71 Å. There is one shorter (2.50 Å) and one longer (2.58 Å) Na(2)-O(8) bond length. The Na(2)-F(2) bond length is 2.35 Å. There is one shorter (2.40 Å) and one longer (2.48 Å) Na(2)-F(1) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), two equivalent O(7), and one F(1) atom. The Na(3)-O(1) bond length is 2.40 Å. The Na(3)-O(2) bond length is 2.76 Å. The Na(3)-O(3) bond length is 2.48 Å. The Na(3)-O(4) bond length is 2.51 Å. There is one shorter (2.46 Å) and one longer (2.95 Å) Na(3)-O(7) bond length. The Na(3)-F(1) bond length is 2.39 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(6), two equivalent F(1), and two equivalent F(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(2)O5F octahedra, corners with two equivalent S(2)O4 tetrahedra, and edges with two equivalent Na(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Mn(1)-O(6) bond lengths are 1.97 Å. Both Mn(1)-F(1) bond lengths are 1.89 Å. Both Mn(1)-F(2) bond lengths are 2.17 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one F(2) atom to form MnO5F octahedra that share  a cornercorner with one Na(1)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent S(2)O4 tetrahedra, and corners with three equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-68°. The Mn(2)-O(2) bond length is 2.20 Å. The Mn(2)-O(3) bond length is 2.19 Å. The Mn(2)-O(4) bond length is 2.18 Å. The Mn(2)-O(5) bond length is 2.17 Å. The Mn(2)-O(7) bond length is 2.28 Å. The Mn(2)-F(2) bond length is 2.16 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O4F2 octahedra and corners with three equivalent Mn(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 36-58°. The S(1)-O(2) bond length is 1.50 Å. The S(1)-O(3) bond length is 1.49 Å. The S(1)-O(4) bond length is 1.50 Å. The S(1)-O(8) bond length is 1.49 Å. In the second S site, S(2) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, and corners with two equivalent Mn(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 23-59°. The S(2)-O(1) bond length is 1.46 Å. The S(2)-O(5) bond length is 1.46 Å. The S(2)-O(6) bond length is 1.54 Å. The S(2)-O(7) bond length is 1.50 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one S(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(2), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(3), one Mn(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(2) and one S(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one S(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to two equivalent Na(3), one Mn(2), and one S(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one S(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Na(3), two equivalent Na(2), and one Mn(1) atom to form distorted FNa3Mn trigonal pyramids that share corners with two equivalent F(2)Na2Mn2 tetrahedra,  a cornercorner with one F(1)Na3Mn trigonal pyramid,  an edgeedge with one F(2)Na2Mn2 tetrahedra, and  an edgeedge with one F(1)Na3Mn trigonal pyramid. In the second F site, F(2) is bonded to one Na(1), one Na(2), one Mn(1), and one Mn(2) atom to form FNa2Mn2 tetrahedra that share corners with two equivalent F(2)Na2Mn2 tetrahedra, corners with two equivalent F(1)Na3Mn trigonal pyramids, and  an edgeedge with one F(1)Na3Mn trigonal pyramid.