The material described by Na12Mn3S6(O3F)8 crystallizes in the triclinic P-1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(6), two equivalent O(8), one F(2), and one F(3) atom. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(3), one O(7), one F(1), and one F(2) atom. In the third Na site, Na(3) is bonded to one O(1), one O(12), two equivalent O(9), one F(3), and one F(4) atom to form NaO4F2 octahedra that share  a cornercorner with one Na(5)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra,  an edgeedge with one Na(3)O4F2 octahedra,  an edgeedge with one Mn(2)O2F4 octahedra, and  an edgeedge with one Na(4)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 45-73°. In the fourth Na site, Na(4) is bonded to one O(1), one O(5), one O(8), one F(1), and one F(3) atom to form distorted NaO3F2 trigonal bipyramids that share corners with two equivalent Na(5)O4F2 octahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra,  an edgeedge with one Na(3)O4F2 octahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 69-72°. In the fifth Na site, Na(5) is bonded to one O(2), one O(5), two equivalent O(4), one F(1), and one F(4) atom to form distorted NaO4F2 octahedra that share  a cornercorner with one Na(3)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent S(3)O4 tetrahedra, corners with two equivalent Na(4)O3F2 trigonal bipyramids,  an edgeedge with one Na(5)O4F2 octahedra, and  an edgeedge with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-73°. In the sixth Na site, Na(6) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(6), one F(2), and one F(4) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with two equivalent Na(3)O4F2 octahedra, corners with two equivalent Na(5)O4F2 octahedra, corners with two equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(4)O3F2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-60°. In the second Mn site, Mn(2) is bonded to two equivalent O(12), two equivalent F(2), and two equivalent F(4) atoms to form MnO2F4 octahedra that share corners with two equivalent Na(5)O4F2 octahedra, corners with two equivalent S(3)O4 tetrahedra, and edges with two equivalent Na(3)O4F2 octahedra. The corner-sharing octahedral tilt angles are 44°. In the third Mn site, Mn(3) is bonded to two equivalent O(11), two equivalent O(2), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Na(5)O4F2 octahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and corners with two equivalent S(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one O(10), one O(3), one O(7), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and corners with two equivalent Na(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the second S site, S(2) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Na(3)O4F2 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Na(4)O3F2 trigonal bipyramids, and  an edgeedge with one Na(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the third S site, S(3) is bonded to one O(11), one O(12), one O(4), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Na(3)O4F2 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Na(5)O4F2 octahedra, and  a cornercorner with one Na(4)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 46-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Na(6), and one S(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(5), one Mn(3), and one S(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Na(6), and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(5) and one S(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(4), one Na(5), one Na(6), and one S(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(6), and one S(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Na(2), one Mn(3), and one S(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(4), two equivalent Na(1), and one S(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent Na(3) and one S(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one S(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Mn(3), and one S(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one S(3) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), one Na(4), one Na(5), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. In the second F site, F(2) is bonded to one Na(1), one Na(2), one Na(6), and one Mn(2) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. In the third F site, F(3) is bonded to one Na(1), one Na(3), one Na(4), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. In the fourth F site, F(4) is bonded to one Na(3), one Na(5), one Na(6), and one Mn(2) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. is represented by the CIF file [CIF]
data_Na12Mn3S6(O3F)8
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.676
_cell_length_b   9.708
_cell_length_c   9.797
_cell_angle_alpha   113.801
_cell_angle_beta   105.206
_cell_angle_gamma   109.007
_symmetry_Int_Tables_number   1
_cell_volume   708.795
_cell_formula_units_Z   1
loop_
 _symmetry_equiv_pos_site_id
 _symmetry_equiv_pos_as_xyz
  1  'x, y, z'
loop_
 _atom_site_type_symbol
 _atom_site_label
 _atom_site_symmetry_multiplicity
 _atom_site_fract_x
 _atom_site_fract_y
 _atom_site_fract_z
 _atom_site_occupancy
  Na  Na0  1  0.696  0.050  0.204  1.0
  Na  Na1  1  0.304  0.950  0.796  1.0
  Na  Na2  1  0.155  0.145  0.441  1.0
  Na  Na3  1  0.845  0.855  0.559  1.0
  Na  Na4  1  0.112  0.679  0.985  1.0
  Na  Na5  1  0.888  0.321  0.015  1.0
  Na  Na6  1  0.660  0.425  0.215  1.0
  Na  Na7  1  0.340  0.575  0.785  1.0
  Na  Na8  1  0.672  0.500  0.634  1.0
  Na  Na9  1  0.328  0.500  0.366  1.0
  Na  Na10  1  0.781  0.717  0.083  1.0
  Na  Na11  1  0.219  0.283  0.917  1.0
  Mn  Mn12  1  0.000  0.500  0.500  1.0
  Mn  Mn13  1  0.000  0.000  0.000  1.0
  Mn  Mn14  1  0.500  0.000  0.500  1.0
  S  S15  1  0.090  0.762  0.357  1.0
  S  S16  1  0.910  0.238  0.643  1.0
  S  S17  1  0.536  0.335  0.816  1.0
  S  S18  1  0.464  0.665  0.184  1.0
  S  S19  1  0.395  0.127  0.228  1.0
  S  S20  1  0.605  0.873  0.772  1.0
  O  O21  1  0.674  0.390  0.973  1.0
  O  O22  1  0.326  0.610  0.027  1.0
  O  O23  1  0.569  0.257  0.670  1.0
  O  O24  1  0.431  0.743  0.330  1.0
  O  O25  1  0.948  0.791  0.358  1.0
  O  O26  1  0.052  0.209  0.642  1.0
  O  O27  1  0.419  0.290  0.362  1.0
  O  O28  1  0.581  0.710  0.638  1.0
  O  O29  1  0.532  0.492  0.828  1.0
  O  O30  1  0.468  0.508  0.172  1.0
  O  O31  1  0.378  0.211  0.789  1.0
  O  O32  1  0.622  0.789  0.211  1.0
  O  O33  1  0.234  0.930  0.421  1.0
  O  O34  1  0.766  0.070  0.579  1.0
  O  O35  1  0.451  0.152  0.108  1.0
  O  O36  1  0.549  0.848  0.892  1.0
  O  O37  1  0.047  0.632  0.185  1.0
  O  O38  1  0.953  0.368  0.815  1.0
  O  O39  1  0.137  0.704  0.474  1.0
  O  O40  1  0.863  0.296  0.526  1.0
  O  O41  1  0.488  0.057  0.301  1.0
  O  O42  1  0.512  0.943  0.699  1.0
  O  O43  1  0.215  0.995  0.134  1.0
  O  O44  1  0.785  0.005  0.866  1.0
  F  F45  1  0.834  0.571  0.505  1.0
  F  F46  1  0.166  0.429  0.495  1.0
  F  F47  1  0.938  0.017  0.175  1.0
  F  F48  1  0.062  0.983  0.825  1.0
  F  F49  1  0.864  0.343  0.265  1.0
  F  F50  1  0.136  0.657  0.735  1.0
  F  F51  1  0.896  0.756  0.903  1.0
  F  F52  1  0.104  0.244  0.097  1.0
[/CIF]
.
The material described by Na12Mn3S6(O3F)8 crystallizes in the triclinic P-1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(6), two equivalent O(8), one F(2), and one F(3) atom. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(3), one O(7), one F(1), and one F(2) atom. In the third Na site, Na(3) is bonded to one O(1), one O(12), two equivalent O(9), one F(3), and one F(4) atom to form NaO4F2 octahedra that share  a cornercorner with one Na(5)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra,  an edgeedge with one Na(3)O4F2 octahedra,  an edgeedge with one Mn(2)O2F4 octahedra, and  an edgeedge with one Na(4)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 45-73°. In the fourth Na site, Na(4) is bonded to one O(1), one O(5), one O(8), one F(1), and one F(3) atom to form distorted NaO3F2 trigonal bipyramids that share corners with two equivalent Na(5)O4F2 octahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra,  an edgeedge with one Na(3)O4F2 octahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 69-72°. In the fifth Na site, Na(5) is bonded to one O(2), one O(5), two equivalent O(4), one F(1), and one F(4) atom to form distorted NaO4F2 octahedra that share  a cornercorner with one Na(3)O4F2 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent S(3)O4 tetrahedra, corners with two equivalent Na(4)O3F2 trigonal bipyramids,  an edgeedge with one Na(5)O4F2 octahedra, and  an edgeedge with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-73°. In the sixth Na site, Na(6) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(6), one F(2), and one F(4) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with two equivalent Na(3)O4F2 octahedra, corners with two equivalent Na(5)O4F2 octahedra, corners with two equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(4)O3F2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-60°. In the second Mn site, Mn(2) is bonded to two equivalent O(12), two equivalent F(2), and two equivalent F(4) atoms to form MnO2F4 octahedra that share corners with two equivalent Na(5)O4F2 octahedra, corners with two equivalent S(3)O4 tetrahedra, and edges with two equivalent Na(3)O4F2 octahedra. The corner-sharing octahedral tilt angles are 44°. In the third Mn site, Mn(3) is bonded to two equivalent O(11), two equivalent O(2), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent Na(5)O4F2 octahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, and corners with two equivalent S(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one O(10), one O(3), one O(7), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and corners with two equivalent Na(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the second S site, S(2) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Na(3)O4F2 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Na(4)O3F2 trigonal bipyramids, and  an edgeedge with one Na(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the third S site, S(3) is bonded to one O(11), one O(12), one O(4), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Na(3)O4F2 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Na(5)O4F2 octahedra, and  a cornercorner with one Na(4)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 46-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Na(6), and one S(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(5), one Mn(3), and one S(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Na(6), and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(5) and one S(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(4), one Na(5), one Na(6), and one S(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(6), and one S(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Na(2), one Mn(3), and one S(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(4), two equivalent Na(1), and one S(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent Na(3) and one S(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one S(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Mn(3), and one S(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one S(3) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), one Na(4), one Na(5), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. In the second F site, F(2) is bonded to one Na(1), one Na(2), one Na(6), and one Mn(2) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. In the third F site, F(3) is bonded to one Na(1), one Na(3), one Na(4), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. In the fourth F site, F(4) is bonded to one Na(3), one Na(5), one Na(6), and one Mn(2) atom to form a mixture of distorted edge and corner-sharing FNa3Mn tetrahedra. is represented by the CIF file [CIF]
data_Na12Mn3S6(O3F)8
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.676
_cell_length_b   9.708
_cell_length_c   9.797
_cell_angle_alpha   113.801
_cell_angle_beta   105.206
_cell_angle_gamma   109.007
_symmetry_Int_Tables_number   1
_cell_volume   708.795
_cell_formula_units_Z   1
loop_
 _symmetry_equiv_pos_site_id
 _symmetry_equiv_pos_as_xyz
  1  'x, y, z'
loop_
 _atom_site_type_symbol
 _atom_site_label
 _atom_site_symmetry_multiplicity
 _atom_site_fract_x
 _atom_site_fract_y
 _atom_site_fract_z
 _atom_site_occupancy
  Na  Na0  1  0.696  0.050  0.204  1.0
  Na  Na1  1  0.304  0.950  0.796  1.0
  Na  Na2  1  0.155  0.145  0.441  1.0
  Na  Na3  1  0.845  0.855  0.559  1.0
  Na  Na4  1  0.112  0.679  0.985  1.0
  Na  Na5  1  0.888  0.321  0.015  1.0
  Na  Na6  1  0.660  0.425  0.215  1.0
  Na  Na7  1  0.340  0.575  0.785  1.0
  Na  Na8  1  0.672  0.500  0.634  1.0
  Na  Na9  1  0.328  0.500  0.366  1.0
  Na  Na10  1  0.781  0.717  0.083  1.0
  Na  Na11  1  0.219  0.283  0.917  1.0
  Mn  Mn12  1  0.000  0.500  0.500  1.0
  Mn  Mn13  1  0.000  0.000  0.000  1.0
  Mn  Mn14  1  0.500  0.000  0.500  1.0
  S  S15  1  0.090  0.762  0.357  1.0
  S  S16  1  0.910  0.238  0.643  1.0
  S  S17  1  0.536  0.335  0.816  1.0
  S  S18  1  0.464  0.665  0.184  1.0
  S  S19  1  0.395  0.127  0.228  1.0
  S  S20  1  0.605  0.873  0.772  1.0
  O  O21  1  0.674  0.390  0.973  1.0
  O  O22  1  0.326  0.610  0.027  1.0
  O  O23  1  0.569  0.257  0.670  1.0
  O  O24  1  0.431  0.743  0.330  1.0
  O  O25  1  0.948  0.791  0.358  1.0
  O  O26  1  0.052  0.209  0.642  1.0
  O  O27  1  0.419  0.290  0.362  1.0
  O  O28  1  0.581  0.710  0.638  1.0
  O  O29  1  0.532  0.492  0.828  1.0
  O  O30  1  0.468  0.508  0.172  1.0
  O  O31  1  0.378  0.211  0.789  1.0
  O  O32  1  0.622  0.789  0.211  1.0
  O  O33  1  0.234  0.930  0.421  1.0
  O  O34  1  0.766  0.070  0.579  1.0
  O  O35  1  0.451  0.152  0.108  1.0
  O  O36  1  0.549  0.848  0.892  1.0
  O  O37  1  0.047  0.632  0.185  1.0
  O  O38  1  0.953  0.368  0.815  1.0
  O  O39  1  0.137  0.704  0.474  1.0
  O  O40  1  0.863  0.296  0.526  1.0
  O  O41  1  0.488  0.057  0.301  1.0
  O  O42  1  0.512  0.943  0.699  1.0
  O  O43  1  0.215  0.995  0.134  1.0
  O  O44  1  0.785  0.005  0.866  1.0
  F  F45  1  0.834  0.571  0.505  1.0
  F  F46  1  0.166  0.429  0.495  1.0
  F  F47  1  0.938  0.017  0.175  1.0
  F  F48  1  0.062  0.983  0.825  1.0
  F  F49  1  0.864  0.343  0.265  1.0
  F  F50  1  0.136  0.657  0.735  1.0
  F  F51  1  0.896  0.756  0.903  1.0
  F  F52  1  0.104  0.244  0.097  1.0
[/CIF]
.