Mn12O5F19 crystallizes in the triclinic P1 space group. There are twelve inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 7-coordinate geometry to one O(2), one F(10), one F(15), one F(18), one F(2), one F(5), and one F(8) atom. In the second Mn site, Mn(2) is bonded to one O(2), one O(5), one F(1), one F(19), and one F(2) atom to form corner-sharing MnO2F3 trigonal bipyramids. In the third Mn site, Mn(3) is bonded to one O(3), one F(1), one F(11), one F(14), one F(19), one F(4), and one F(6) atom to form distorted corner-sharing MnOF6 pentagonal bipyramids. In the fourth Mn site, Mn(4) is bonded in a 7-coordinate geometry to one O(3), one F(12), one F(14), one F(17), one F(3), one F(4), and one F(7) atom. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(4), one F(13), one F(16), one F(17), and one F(3) atom to form distorted corner-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. In the sixth Mn site, Mn(6) is bonded in a 7-coordinate geometry to one O(1), one F(13), one F(16), one F(18), one F(5), one F(8), and one F(9) atom. In the seventh Mn site, Mn(7) is bonded in a 8-coordinate geometry to one O(2), one O(5), one F(1), one F(11), one F(15), one F(19), one F(2), and one F(6) atom. In the eighth Mn site, Mn(8) is bonded in a 6-coordinate geometry to one O(2), one O(5), one F(10), one F(15), one F(5), and one F(8) atom. In the ninth Mn site, Mn(9) is bonded to one O(1), one O(4), one F(13), one F(3), one F(7), and one F(9) atom to form distorted corner-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. In the tenth Mn site, Mn(10) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(12), one F(14), one F(17), and one F(7) atom. In the eleventh Mn site, Mn(11) is bonded in a 7-coordinate geometry to one O(3), one F(1), one F(11), one F(12), one F(14), one F(4), and one F(6) atom. In the twelfth Mn site, Mn(12) is bonded in a 6-coordinate geometry to one O(1), one F(13), one F(18), one F(5), one F(8), and one F(9) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Mn(12), one Mn(5), one Mn(6), and one Mn(9) atom to form distorted OMn4 tetrahedra that share corners with two equivalent F(5)Mn4 tetrahedra,  an edgeedge with one F(8)Mn4 tetrahedra, and edges with two equivalent F(13)Mn4 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), one Mn(7), and one Mn(8) atom. In the third O site, O(3) is bonded to one Mn(10), one Mn(11), one Mn(3), and one Mn(4) atom to form OMn4 tetrahedra that share edges with two equivalent F(14)Mn4 trigonal pyramids. In the fourth O site, O(4) is bonded in a 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(2), one Mn(7), and one Mn(8) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Mn(11), one Mn(2), one Mn(3), and one Mn(7) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(7) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(4), one Mn(5), and one Mn(9) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(11), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom to form FMn4 tetrahedra that share corners with two equivalent O(1)Mn4 tetrahedra, corners with two equivalent F(13)Mn4 tetrahedra, and edges with two equivalent F(8)Mn4 tetrahedra. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Mn(11), one Mn(3), and one Mn(7) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Mn(10), one Mn(4), and one Mn(9) atom. In the eighth F site, F(8) is bonded to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom to form distorted FMn4 tetrahedra that share corners with two equivalent F(13)Mn4 tetrahedra,  an edgeedge with one O(1)Mn4 tetrahedra, and edges with two equivalent F(5)Mn4 tetrahedra. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Mn(12), one Mn(6), and one Mn(9) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one Mn(1) and one Mn(8) atom. In the eleventh F site, F(11) is bonded in a trigonal non-coplanar geometry to one Mn(11), one Mn(3), and one Mn(7) atom. In the twelfth F site, F(12) is bonded in a trigonal non-coplanar geometry to one Mn(10), one Mn(11), and one Mn(4) atom. In the thirteenth F site, F(13) is bonded to one Mn(12), one Mn(5), one Mn(6), and one Mn(9) atom to form FMn4 tetrahedra that share corners with two equivalent F(5)Mn4 tetrahedra, corners with two equivalent F(8)Mn4 tetrahedra, and edges with two equivalent O(1)Mn4 tetrahedra. In the fourteenth F site, F(14) is bonded to one Mn(10), one Mn(11), one Mn(3), and one Mn(4) atom to form distorted FMn4 trigonal pyramids that share edges with two equivalent O(3)Mn4 tetrahedra. In the fifteenth F site, F(15) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(7), and one Mn(8) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 150 degrees geometry to one Mn(5) and one Mn(6) atom. In the seventeenth F site, F(17) is bonded in a 3-coordinate geometry to one Mn(10), one Mn(4), and one Mn(5) atom. In the eighteenth F site, F(18) is bonded in a trigonal planar geometry to one Mn(1), one Mn(12), and one Mn(6) atom. In the nineteenth F site, F(19) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), 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 in a 7-coordinate geometry to one O(2), one F(10), one F(15), one F(18), one F(2), one F(5), and one F(8) atom. The Mn(1)-O(2) bond length is 2.10 Å. The Mn(1)-F(10) bond length is 2.13 Å. The Mn(1)-F(15) bond length is 2.19 Å. The Mn(1)-F(18) bond length is 2.11 Å. The Mn(1)-F(2) bond length is 2.10 Å. The Mn(1)-F(5) bond length is 2.29 Å. The Mn(1)-F(8) bond length is 2.56 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(5), one F(1), one F(19), and one F(2) atom to form corner-sharing MnO2F3 trigonal bipyramids. The Mn(2)-O(2) bond length is 1.88 Å. The Mn(2)-O(5) bond length is 1.94 Å. The Mn(2)-F(1) bond length is 2.04 Å. The Mn(2)-F(19) bond length is 1.96 Å. The Mn(2)-F(2) bond length is 2.20 Å. In the third Mn site, Mn(3) is bonded to one O(3), one F(1), one F(11), one F(14), one F(19), one F(4), and one F(6) atom to form distorted corner-sharing MnOF6 pentagonal bipyramids. The Mn(3)-O(3) bond length is 2.11 Å. The Mn(3)-F(1) bond length is 2.23 Å. The Mn(3)-F(11) bond length is 2.20 Å. The Mn(3)-F(14) bond length is 2.31 Å. The Mn(3)-F(19) bond length is 2.10 Å. The Mn(3)-F(4) bond length is 2.08 Å. The Mn(3)-F(6) bond length is 2.36 Å. In the fourth Mn site, Mn(4) is bonded in a 7-coordinate geometry to one O(3), one F(12), one F(14), one F(17), one F(3), one F(4), and one F(7) atom. The Mn(4)-O(3) bond length is 1.99 Å. The Mn(4)-F(12) bond length is 2.29 Å. The Mn(4)-F(14) bond length is 2.15 Å. The Mn(4)-F(17) bond length is 2.10 Å. The Mn(4)-F(3) bond length is 2.12 Å. The Mn(4)-F(4) bond length is 2.04 Å. The Mn(4)-F(7) bond length is 2.60 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(4), one F(13), one F(16), one F(17), and one F(3) atom to form distorted corner-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. The Mn(5)-O(1) bond length is 1.98 Å. The Mn(5)-O(4) bond length is 1.92 Å. The Mn(5)-F(13) bond length is 2.43 Å. The Mn(5)-F(16) bond length is 1.91 Å. The Mn(5)-F(17) bond length is 1.96 Å. The Mn(5)-F(3) bond length is 2.26 Å. In the sixth Mn site, Mn(6) is bonded in a 7-coordinate geometry to one O(1), one F(13), one F(16), one F(18), one F(5), one F(8), and one F(9) atom. The Mn(6)-O(1) bond length is 2.24 Å. The Mn(6)-F(13) bond length is 2.26 Å. The Mn(6)-F(16) bond length is 2.12 Å. The Mn(6)-F(18) bond length is 2.16 Å. The Mn(6)-F(5) bond length is 2.34 Å. The Mn(6)-F(8) bond length is 2.22 Å. The Mn(6)-F(9) bond length is 2.37 Å. In the seventh Mn site, Mn(7) is bonded in a 8-coordinate geometry to one O(2), one O(5), one F(1), one F(11), one F(15), one F(19), one F(2), and one F(6) atom. The Mn(7)-O(2) bond length is 2.72 Å. The Mn(7)-O(5) bond length is 2.13 Å. The Mn(7)-F(1) bond length is 2.66 Å. The Mn(7)-F(11) bond length is 2.26 Å. The Mn(7)-F(15) bond length is 2.12 Å. The Mn(7)-F(19) bond length is 2.30 Å. The Mn(7)-F(2) bond length is 2.24 Å. The Mn(7)-F(6) bond length is 2.13 Å. In the eighth Mn site, Mn(8) is bonded in a 6-coordinate geometry to one O(2), one O(5), one F(10), one F(15), one F(5), and one F(8) atom. The Mn(8)-O(2) bond length is 1.99 Å. The Mn(8)-O(5) bond length is 1.89 Å. The Mn(8)-F(10) bond length is 1.98 Å. The Mn(8)-F(15) bond length is 2.18 Å. The Mn(8)-F(5) bond length is 2.11 Å. The Mn(8)-F(8) bond length is 2.25 Å. In the ninth Mn site, Mn(9) is bonded to one O(1), one O(4), one F(13), one F(3), one F(7), and one F(9) atom to form distorted corner-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. The Mn(9)-O(1) bond length is 2.00 Å. The Mn(9)-O(4) bond length is 1.93 Å. The Mn(9)-F(13) bond length is 2.23 Å. The Mn(9)-F(3) bond length is 2.33 Å. The Mn(9)-F(7) bond length is 1.92 Å. The Mn(9)-F(9) bond length is 1.93 Å. In the tenth Mn site, Mn(10) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(12), one F(14), one F(17), and one F(7) atom. The Mn(10)-O(3) bond length is 2.10 Å. The Mn(10)-O(4) bond length is 2.10 Å. The Mn(10)-F(12) bond length is 2.10 Å. The Mn(10)-F(14) bond length is 2.26 Å. The Mn(10)-F(17) bond length is 2.35 Å. The Mn(10)-F(7) bond length is 2.22 Å. In the eleventh Mn site, Mn(11) is bonded in a 7-coordinate geometry to one O(3), one F(1), one F(11), one F(12), one F(14), one F(4), and one F(6) atom. The Mn(11)-O(3) bond length is 2.16 Å. The Mn(11)-F(1) bond length is 2.25 Å. The Mn(11)-F(11) bond length is 2.11 Å. The Mn(11)-F(12) bond length is 2.08 Å. The Mn(11)-F(14) bond length is 2.45 Å. The Mn(11)-F(4) bond length is 2.29 Å. The Mn(11)-F(6) bond length is 2.16 Å. In the twelfth Mn site, Mn(12) is bonded in a 6-coordinate geometry to one O(1), one F(13), one F(18), one F(5), one F(8), and one F(9) atom. The Mn(12)-O(1) bond length is 2.29 Å. The Mn(12)-F(13) bond length is 2.19 Å. The Mn(12)-F(18) bond length is 2.13 Å. The Mn(12)-F(5) bond length is 2.26 Å. The Mn(12)-F(8) bond length is 2.16 Å. The Mn(12)-F(9) bond length is 2.11 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Mn(12), one Mn(5), one Mn(6), and one Mn(9) atom to form distorted OMn4 tetrahedra that share corners with two equivalent F(5)Mn4 tetrahedra,  an edgeedge with one F(8)Mn4 tetrahedra, and edges with two equivalent F(13)Mn4 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), one Mn(7), and one Mn(8) atom. In the third O site, O(3) is bonded to one Mn(10), one Mn(11), one Mn(3), and one Mn(4) atom to form OMn4 tetrahedra that share edges with two equivalent F(14)Mn4 trigonal pyramids. In the fourth O site, O(4) is bonded in a 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(2), one Mn(7), and one Mn(8) atom. There are nineteen inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Mn(11), one Mn(2), one Mn(3), and one Mn(7) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(7) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(4), one Mn(5), and one Mn(9) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(11), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom to form FMn4 tetrahedra that share corners with two equivalent O(1)Mn4 tetrahedra, corners with two equivalent F(13)Mn4 tetrahedra, and edges with two equivalent F(8)Mn4 tetrahedra. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Mn(11), one Mn(3), and one Mn(7) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Mn(10), one Mn(4), and one Mn(9) atom. In the eighth F site, F(8) is bonded to one Mn(1), one Mn(12), one Mn(6), and one Mn(8) atom to form distorted FMn4 tetrahedra that share corners with two equivalent F(13)Mn4 tetrahedra,  an edgeedge with one O(1)Mn4 tetrahedra, and edges with two equivalent F(5)Mn4 tetrahedra. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Mn(12), one Mn(6), and one Mn(9) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one Mn(1) and one Mn(8) atom. In the eleventh F site, F(11) is bonded in a trigonal non-coplanar geometry to one Mn(11), one Mn(3), and one Mn(7) atom. In the twelfth F site, F(12) is bonded in a trigonal non-coplanar geometry to one Mn(10), one Mn(11), and one Mn(4) atom. In the thirteenth F site, F(13) is bonded to one Mn(12), one Mn(5), one Mn(6), and one Mn(9) atom to form FMn4 tetrahedra that share corners with two equivalent F(5)Mn4 tetrahedra, corners with two equivalent F(8)Mn4 tetrahedra, and edges with two equivalent O(1)Mn4 tetrahedra. In the fourteenth F site, F(14) is bonded to one Mn(10), one Mn(11), one Mn(3), and one Mn(4) atom to form distorted FMn4 trigonal pyramids that share edges with two equivalent O(3)Mn4 tetrahedra. In the fifteenth F site, F(15) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(7), and one Mn(8) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 150 degrees geometry to one Mn(5) and one Mn(6) atom. In the seventeenth F site, F(17) is bonded in a 3-coordinate geometry to one Mn(10), one Mn(4), and one Mn(5) atom. In the eighteenth F site, F(18) is bonded in a trigonal planar geometry to one Mn(1), one Mn(12), and one Mn(6) atom. In the nineteenth F site, F(19) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(3), and one Mn(7) atom.