CaMn6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one O(2), one O(3), one F(1), and one F(6) atom to form distorted CaO3F2 trigonal bipyramids that share  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra, corners with two equivalent Mn(5)O2F4 octahedra,  a cornercorner with one Mn(4)O2F3 square pyramid, corners with two equivalent Mn(2)OF4 trigonal bipyramids, and  an edgeedge with one Mn(4)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 29-81°. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom to form MnO2F4 octahedra that share  a cornercorner with one Mn(5)O2F4 octahedra, corners with two equivalent Mn(4)O2F3 square pyramids,  a cornercorner with one Ca(1)O3F2 trigonal bipyramid, corners with two equivalent Mn(2)OF4 trigonal bipyramids,  an edgeedge with one Mn(3)O2F4 octahedra, and  an edgeedge with one Mn(5)O2F4 octahedra. The corner-sharing octahedral tilt angles are 26°. In the second Mn site, Mn(2) is bonded to one O(1), one F(4), one F(5), one F(6), and one F(8) atom to form distorted MnOF4 trigonal bipyramids that share  a cornercorner with one Mn(3)O2F4 octahedra, corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(5)O2F4 octahedra,  a cornercorner with one Mn(4)O2F3 square pyramid, corners with two equivalent Ca(1)O3F2 trigonal bipyramids, and  an edgeedge with one Mn(4)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 44-74°. In the third Mn site, Mn(3) is bonded to one O(3), one O(4), one F(1), one F(3), one F(4), and one F(7) atom to form MnO2F4 octahedra that share  a cornercorner with one Mn(5)O2F4 octahedra, corners with two equivalent Mn(4)O2F3 square pyramids,  a cornercorner with one Mn(2)OF4 trigonal bipyramid, corners with two equivalent Ca(1)O3F2 trigonal bipyramids,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Mn(5)O2F4 octahedra. The corner-sharing octahedral tilt angles are 35°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), and one F(8) atom to form distorted MnO2F3 square pyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra,  a cornercorner with one Ca(1)O3F2 trigonal bipyramid,  a cornercorner with one Mn(2)OF4 trigonal bipyramid,  an edgeedge with one Ca(1)O3F2 trigonal bipyramid, and  an edgeedge with one Mn(2)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-61°. In the fifth Mn site, Mn(5) is bonded to one O(3), one O(4), one F(2), one F(5), one F(6), and one F(7) atom to form distorted MnO2F4 octahedra that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(3)O2F4 octahedra, corners with two equivalent Ca(1)O3F2 trigonal bipyramids, corners with two equivalent Mn(2)OF4 trigonal bipyramids,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. In the sixth Mn site, Mn(6) is bonded in a 5-coordinate geometry to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a tetrahedral geometry to one Ca(1), one Mn(2), one Mn(4), and one Mn(6) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Mn(1), and one Mn(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Mn(3), and one Mn(4) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), one Mn(5), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Mn(2), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a T-shaped geometry to one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(4), and one Mn(6) atom.
CaMn6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one O(2), one O(3), one F(1), and one F(6) atom to form distorted CaO3F2 trigonal bipyramids that share  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra, corners with two equivalent Mn(5)O2F4 octahedra,  a cornercorner with one Mn(4)O2F3 square pyramid, corners with two equivalent Mn(2)OF4 trigonal bipyramids, and  an edgeedge with one Mn(4)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 29-81°. The Ca(1)-O(1) bond length is 2.30 Å. The Ca(1)-O(2) bond length is 2.31 Å. The Ca(1)-O(3) bond length is 2.27 Å. The Ca(1)-F(1) bond length is 2.37 Å. The Ca(1)-F(6) bond length is 2.29 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom to form MnO2F4 octahedra that share  a cornercorner with one Mn(5)O2F4 octahedra, corners with two equivalent Mn(4)O2F3 square pyramids,  a cornercorner with one Ca(1)O3F2 trigonal bipyramid, corners with two equivalent Mn(2)OF4 trigonal bipyramids,  an edgeedge with one Mn(3)O2F4 octahedra, and  an edgeedge with one Mn(5)O2F4 octahedra. The corner-sharing octahedral tilt angles are 26°. The Mn(1)-O(2) bond length is 1.86 Å. The Mn(1)-O(4) bond length is 1.96 Å. The Mn(1)-F(2) bond length is 2.16 Å. The Mn(1)-F(3) bond length is 2.06 Å. The Mn(1)-F(5) bond length is 2.07 Å. The Mn(1)-F(8) bond length is 2.30 Å. In the second Mn site, Mn(2) is bonded to one O(1), one F(4), one F(5), one F(6), and one F(8) atom to form distorted MnOF4 trigonal bipyramids that share  a cornercorner with one Mn(3)O2F4 octahedra, corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(5)O2F4 octahedra,  a cornercorner with one Mn(4)O2F3 square pyramid, corners with two equivalent Ca(1)O3F2 trigonal bipyramids, and  an edgeedge with one Mn(4)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 44-74°. The Mn(2)-O(1) bond length is 2.05 Å. The Mn(2)-F(4) bond length is 2.14 Å. The Mn(2)-F(5) bond length is 2.31 Å. The Mn(2)-F(6) bond length is 2.20 Å. The Mn(2)-F(8) bond length is 2.21 Å. In the third Mn site, Mn(3) is bonded to one O(3), one O(4), one F(1), one F(3), one F(4), and one F(7) atom to form MnO2F4 octahedra that share  a cornercorner with one Mn(5)O2F4 octahedra, corners with two equivalent Mn(4)O2F3 square pyramids,  a cornercorner with one Mn(2)OF4 trigonal bipyramid, corners with two equivalent Ca(1)O3F2 trigonal bipyramids,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Mn(5)O2F4 octahedra. The corner-sharing octahedral tilt angles are 35°. The Mn(3)-O(3) bond length is 1.88 Å. The Mn(3)-O(4) bond length is 1.92 Å. The Mn(3)-F(1) bond length is 2.04 Å. The Mn(3)-F(3) bond length is 2.16 Å. The Mn(3)-F(4) bond length is 2.14 Å. The Mn(3)-F(7) bond length is 2.05 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), and one F(8) atom to form distorted MnO2F3 square pyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra,  a cornercorner with one Ca(1)O3F2 trigonal bipyramid,  a cornercorner with one Mn(2)OF4 trigonal bipyramid,  an edgeedge with one Ca(1)O3F2 trigonal bipyramid, and  an edgeedge with one Mn(2)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-61°. The Mn(4)-O(1) bond length is 2.09 Å. The Mn(4)-O(2) bond length is 2.03 Å. The Mn(4)-F(1) bond length is 2.13 Å. The Mn(4)-F(4) bond length is 2.18 Å. The Mn(4)-F(8) bond length is 2.24 Å. In the fifth Mn site, Mn(5) is bonded to one O(3), one O(4), one F(2), one F(5), one F(6), and one F(7) atom to form distorted MnO2F4 octahedra that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(3)O2F4 octahedra, corners with two equivalent Ca(1)O3F2 trigonal bipyramids, corners with two equivalent Mn(2)OF4 trigonal bipyramids,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. The Mn(5)-O(3) bond length is 2.05 Å. The Mn(5)-O(4) bond length is 1.99 Å. The Mn(5)-F(2) bond length is 2.17 Å. The Mn(5)-F(5) bond length is 2.53 Å. The Mn(5)-F(6) bond length is 2.44 Å. The Mn(5)-F(7) bond length is 2.18 Å. In the sixth Mn site, Mn(6) is bonded in a 5-coordinate geometry to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom. The Mn(6)-O(1) bond length is 2.03 Å. The Mn(6)-F(2) bond length is 2.14 Å. The Mn(6)-F(3) bond length is 2.09 Å. The Mn(6)-F(5) bond length is 2.75 Å. The Mn(6)-F(7) bond length is 2.08 Å. The Mn(6)-F(8) bond length is 2.42 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a tetrahedral geometry to one Ca(1), one Mn(2), one Mn(4), and one Mn(6) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Mn(1), and one Mn(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Mn(3), and one Mn(4) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), one Mn(5), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Mn(2), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a T-shaped geometry to one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(4), and one Mn(6) atom.