Mn12O5F19 crystallizes in the triclinic P1 space group. There are twelve inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one F(10), one F(11), one F(15), one F(18), one F(2), and one F(5) atom to form distorted MnOF6 pentagonal bipyramids that share  a cornercorner with one Mn(6)O2F4 octahedra, corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(7)OF5 octahedra, and  an edgeedge with one Mn(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. In the second Mn site, Mn(2) is bonded to one O(1), one O(5), one F(1), one F(11), one F(15), and one F(7) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(11)O2F4 octahedra, corners with two equivalent Mn(3)OF5 octahedra, corners with two equivalent Mn(1)OF6 pentagonal bipyramids, and edges with two equivalent Mn(7)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. In the third Mn site, Mn(3) is bonded to one O(1), one F(1), one F(12), one F(14), one F(19), and one F(4) atom to form distorted MnOF5 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(7)OF5 octahedra, and edges with two equivalent Mn(11)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. In the fourth Mn site, Mn(4) is bonded in a 6-coordinate geometry to one F(12), one F(14), one F(17), one F(3), one F(8), and one F(9) atom. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(4), one F(13), one F(16), one F(17), one F(3), and one F(6) atom. In the sixth Mn site, Mn(6) is bonded to one O(2), one O(3), one F(16), one F(18), one F(5), and one F(6) atom to form a mixture of distorted corner and edge-sharing MnO2F4 octahedra. In the seventh Mn site, Mn(7) is bonded to one O(5), one F(1), one F(15), one F(19), one F(2), and one F(7) atom to form MnOF5 octahedra that share corners with two equivalent Mn(11)O2F4 octahedra, corners with two equivalent Mn(3)OF5 octahedra, corners with two equivalent Mn(1)OF6 pentagonal bipyramids, and edges with two equivalent Mn(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. In the eighth Mn site, Mn(8) is bonded in a 7-coordinate geometry to one O(2), one F(10), one F(11), one F(18), one F(2), one F(5), and one F(7) atom. In the ninth Mn site, Mn(9) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(13), one F(3), one F(6), and one F(8) atom. In the tenth Mn site, Mn(10) is bonded in a 6-coordinate geometry to one O(4), one F(14), one F(17), one F(3), one F(4), and one F(8) atom. In the eleventh Mn site, Mn(11) is bonded to one O(1), one O(5), one F(12), one F(19), one F(4), and one F(9) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(7)OF5 octahedra, and edges with two equivalent Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. In the twelfth Mn site, Mn(12) is bonded in a 8-coordinate geometry to one O(2), one O(3), one F(10), one F(13), one F(16), one F(18), one F(5), and one F(6) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(11), one Mn(2), and one Mn(3) atom. In the second O site, O(2) is bonded in a tetrahedral geometry to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mn(12), one Mn(6), and one Mn(9) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(5), and one Mn(9) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(11), one Mn(2), and one Mn(7) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(7) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(7), and one Mn(8) atom. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Mn(10), one Mn(4), one Mn(5), and one Mn(9) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(11), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Mn(12), one Mn(5), one Mn(6), and one Mn(9) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(7), and one Mn(8) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(4), and one Mn(9) atom. In the ninth F site, F(9) is bonded in a bent 120 degrees geometry to one Mn(11) and one Mn(4) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Mn(1), one Mn(12), and one Mn(8) atom. In the eleventh F site, F(11) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(8) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal non-coplanar geometry to one Mn(11), one Mn(3), and one Mn(4) atom. In the thirteenth F site, F(13) is bonded in a trigonal non-coplanar geometry to one Mn(12), one Mn(5), and one Mn(9) atom. In the fourteenth F site, F(14) is bonded in a trigonal planar geometry to one Mn(10), one Mn(3), and one Mn(4) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(7) atom. In the sixteenth F site, F(16) is bonded in a 3-coordinate geometry to one Mn(12), one Mn(5), and one Mn(6) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(4), and one Mn(5) atom. In the eighteenth F site, F(18) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom. In the nineteenth F site, F(19) is bonded in a trigonal planar geometry to one Mn(11), one Mn(3), and one Mn(7) atom.
Mn12O5F19 crystallizes in the triclinic P1 space group. There are twelve inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one F(10), one F(11), one F(15), one F(18), one F(2), and one F(5) atom to form distorted MnOF6 pentagonal bipyramids that share  a cornercorner with one Mn(6)O2F4 octahedra, corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(7)OF5 octahedra, and  an edgeedge with one Mn(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. The Mn(1)-O(2) bond length is 2.22 Å. The Mn(1)-F(10) bond length is 2.34 Å. The Mn(1)-F(11) bond length is 2.25 Å. The Mn(1)-F(15) bond length is 2.14 Å. The Mn(1)-F(18) bond length is 2.26 Å. The Mn(1)-F(2) bond length is 2.31 Å. The Mn(1)-F(5) bond length is 2.12 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(5), one F(1), one F(11), one F(15), and one F(7) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(11)O2F4 octahedra, corners with two equivalent Mn(3)OF5 octahedra, corners with two equivalent Mn(1)OF6 pentagonal bipyramids, and edges with two equivalent Mn(7)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. The Mn(2)-O(1) bond length is 1.94 Å. The Mn(2)-O(5) bond length is 2.05 Å. The Mn(2)-F(1) bond length is 2.21 Å. The Mn(2)-F(11) bond length is 2.14 Å. The Mn(2)-F(15) bond length is 2.09 Å. The Mn(2)-F(7) bond length is 2.08 Å. In the third Mn site, Mn(3) is bonded to one O(1), one F(1), one F(12), one F(14), one F(19), and one F(4) atom to form distorted MnOF5 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(7)OF5 octahedra, and edges with two equivalent Mn(11)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. The Mn(3)-O(1) bond length is 2.00 Å. The Mn(3)-F(1) bond length is 2.11 Å. The Mn(3)-F(12) bond length is 2.26 Å. The Mn(3)-F(14) bond length is 2.06 Å. The Mn(3)-F(19) bond length is 2.14 Å. The Mn(3)-F(4) bond length is 2.14 Å. In the fourth Mn site, Mn(4) is bonded in a 6-coordinate geometry to one F(12), one F(14), one F(17), one F(3), one F(8), and one F(9) atom. The Mn(4)-F(12) bond length is 2.22 Å. The Mn(4)-F(14) bond length is 2.22 Å. The Mn(4)-F(17) bond length is 2.08 Å. The Mn(4)-F(3) bond length is 2.15 Å. The Mn(4)-F(8) bond length is 2.43 Å. The Mn(4)-F(9) bond length is 2.09 Å. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(4), one F(13), one F(16), one F(17), one F(3), and one F(6) atom. The Mn(5)-O(4) bond length is 2.09 Å. The Mn(5)-F(13) bond length is 2.26 Å. The Mn(5)-F(16) bond length is 2.13 Å. The Mn(5)-F(17) bond length is 2.14 Å. The Mn(5)-F(3) bond length is 2.17 Å. The Mn(5)-F(6) bond length is 2.15 Å. In the sixth Mn site, Mn(6) is bonded to one O(2), one O(3), one F(16), one F(18), one F(5), and one F(6) atom to form a mixture of distorted corner and edge-sharing MnO2F4 octahedra. The Mn(6)-O(2) bond length is 1.90 Å. The Mn(6)-O(3) bond length is 1.96 Å. The Mn(6)-F(16) bond length is 1.96 Å. The Mn(6)-F(18) bond length is 1.97 Å. The Mn(6)-F(5) bond length is 2.14 Å. The Mn(6)-F(6) bond length is 2.36 Å. In the seventh Mn site, Mn(7) is bonded to one O(5), one F(1), one F(15), one F(19), one F(2), and one F(7) atom to form MnOF5 octahedra that share corners with two equivalent Mn(11)O2F4 octahedra, corners with two equivalent Mn(3)OF5 octahedra, corners with two equivalent Mn(1)OF6 pentagonal bipyramids, and edges with two equivalent Mn(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. The Mn(7)-O(5) bond length is 1.93 Å. The Mn(7)-F(1) bond length is 2.07 Å. The Mn(7)-F(15) bond length is 2.07 Å. The Mn(7)-F(19) bond length is 2.09 Å. The Mn(7)-F(2) bond length is 1.98 Å. The Mn(7)-F(7) bond length is 2.11 Å. In the eighth Mn site, Mn(8) is bonded in a 7-coordinate geometry to one O(2), one F(10), one F(11), one F(18), one F(2), one F(5), and one F(7) atom. The Mn(8)-O(2) bond length is 2.14 Å. The Mn(8)-F(10) bond length is 2.16 Å. The Mn(8)-F(11) bond length is 2.22 Å. The Mn(8)-F(18) bond length is 2.26 Å. The Mn(8)-F(2) bond length is 2.35 Å. The Mn(8)-F(5) bond length is 2.51 Å. The Mn(8)-F(7) bond length is 2.18 Å. In the ninth Mn site, Mn(9) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(13), one F(3), one F(6), and one F(8) atom. The Mn(9)-O(3) bond length is 1.92 Å. The Mn(9)-O(4) bond length is 1.86 Å. The Mn(9)-F(13) bond length is 2.18 Å. The Mn(9)-F(3) bond length is 2.51 Å. The Mn(9)-F(6) bond length is 2.08 Å. The Mn(9)-F(8) bond length is 1.99 Å. In the tenth Mn site, Mn(10) is bonded in a 6-coordinate geometry to one O(4), one F(14), one F(17), one F(3), one F(4), and one F(8) atom. The Mn(10)-O(4) bond length is 2.09 Å. The Mn(10)-F(14) bond length is 2.18 Å. The Mn(10)-F(17) bond length is 2.27 Å. The Mn(10)-F(3) bond length is 2.27 Å. The Mn(10)-F(4) bond length is 2.19 Å. The Mn(10)-F(8) bond length is 2.18 Å. In the eleventh Mn site, Mn(11) is bonded to one O(1), one O(5), one F(12), one F(19), one F(4), and one F(9) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(7)OF5 octahedra, and edges with two equivalent Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. The Mn(11)-O(1) bond length is 1.95 Å. The Mn(11)-O(5) bond length is 1.91 Å. The Mn(11)-F(12) bond length is 2.05 Å. The Mn(11)-F(19) bond length is 2.25 Å. The Mn(11)-F(4) bond length is 2.07 Å. The Mn(11)-F(9) bond length is 2.10 Å. In the twelfth Mn site, Mn(12) is bonded in a 8-coordinate geometry to one O(2), one O(3), one F(10), one F(13), one F(16), one F(18), one F(5), and one F(6) atom. The Mn(12)-O(2) bond length is 2.16 Å. The Mn(12)-O(3) bond length is 2.14 Å. The Mn(12)-F(10) bond length is 2.13 Å. The Mn(12)-F(13) bond length is 2.15 Å. The Mn(12)-F(16) bond length is 2.51 Å. The Mn(12)-F(18) bond length is 2.69 Å. The Mn(12)-F(5) bond length is 2.37 Å. The Mn(12)-F(6) bond length is 2.70 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(11), one Mn(2), and one Mn(3) atom. In the second O site, O(2) is bonded in a tetrahedral geometry to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mn(12), one Mn(6), and one Mn(9) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(5), and one Mn(9) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(11), one Mn(2), and one Mn(7) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(7) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(7), and one Mn(8) atom. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Mn(10), one Mn(4), one Mn(5), and one Mn(9) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(11), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Mn(12), one Mn(5), one Mn(6), and one Mn(9) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(7), and one Mn(8) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(4), and one Mn(9) atom. In the ninth F site, F(9) is bonded in a bent 120 degrees geometry to one Mn(11) and one Mn(4) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Mn(1), one Mn(12), and one Mn(8) atom. In the eleventh F site, F(11) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(8) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal non-coplanar geometry to one Mn(11), one Mn(3), and one Mn(4) atom. In the thirteenth F site, F(13) is bonded in a trigonal non-coplanar geometry to one Mn(12), one Mn(5), and one Mn(9) atom. In the fourteenth F site, F(14) is bonded in a trigonal planar geometry to one Mn(10), one Mn(3), and one Mn(4) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(7) atom. In the sixteenth F site, F(16) is bonded in a 3-coordinate geometry to one Mn(12), one Mn(5), and one Mn(6) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Mn(10), one Mn(4), and one Mn(5) atom. In the eighteenth F site, F(18) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom. In the nineteenth F site, F(19) is bonded in a trigonal planar geometry to one Mn(11), one Mn(3), and one Mn(7) atom.