CaMn6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one O(2), one F(3), one F(4), one F(5), and one F(8) atom to form CaO2F4 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra, corners with two equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-65°. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), and one F(6) atom to form MnO3F tetrahedra that share  a cornercorner with one Mn(3)O2F4 octahedra,  a cornercorner with one Mn(4)O2F4 octahedra,  a cornercorner with one Mn(6)OF5 octahedra, corners with two equivalent Ca(1)O2F4 octahedra, and  an edgeedge with one Mn(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 32-79°. 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 corners with two equivalent Ca(1)O2F4 octahedra, corners with two equivalent Mn(4)O2F4 octahedra, corners with two equivalent Mn(6)OF5 octahedra, and  a cornercorner with one Mn(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 30-65°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(6), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra,  a cornercorner with one Mn(2)O3F tetrahedra,  an edgeedge with one Mn(6)OF5 octahedra, edges with two equivalent Ca(1)O2F4 octahedra, and  an edgeedge with one Mn(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 30-54°. In the fifth Mn site, Mn(5) is bonded in a 5-coordinate geometry to one O(4), one F(1), one F(2), one F(6), and one F(7) atom. In the sixth Mn site, Mn(6) is bonded to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form MnOF5 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra,  a cornercorner with one Mn(2)O3F tetrahedra,  an edgeedge with one Mn(4)O2F4 octahedra, and edges with two equivalent Ca(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Mn(2), one Mn(4), and one Mn(6) atom to form OCaMn3 trigonal pyramids that share  a cornercorner with one F(8)CaMn3 trigonal pyramid and  an edgeedge with one F(8)CaMn3 trigonal pyramid. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Ca(1), one Mn(1), one Mn(2), and one Mn(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(2) and one Mn(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar 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 T-shaped geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ca(1), 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 Ca(1), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one Mn(1), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(4), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded to one Ca(1), one Mn(1), one Mn(4), and one Mn(6) atom to form distorted FCaMn3 trigonal pyramids that share  a cornercorner with one O(1)CaMn3 trigonal pyramid and  an edgeedge with one O(1)CaMn3 trigonal pyramid.
CaMn6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one O(2), one F(3), one F(4), one F(5), and one F(8) atom to form CaO2F4 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra, corners with two equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-65°. The Ca(1)-O(1) bond length is 2.25 Å. The Ca(1)-O(2) bond length is 2.35 Å. The Ca(1)-F(3) bond length is 2.45 Å. The Ca(1)-F(4) bond length is 2.25 Å. The Ca(1)-F(5) bond length is 2.23 Å. The Ca(1)-F(8) bond length is 2.24 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom. The Mn(1)-O(2) bond length is 2.13 Å. The Mn(1)-O(4) bond length is 2.02 Å. The Mn(1)-F(2) bond length is 2.13 Å. The Mn(1)-F(3) bond length is 2.55 Å. The Mn(1)-F(5) bond length is 2.14 Å. The Mn(1)-F(8) bond length is 2.62 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), and one F(6) atom to form MnO3F tetrahedra that share  a cornercorner with one Mn(3)O2F4 octahedra,  a cornercorner with one Mn(4)O2F4 octahedra,  a cornercorner with one Mn(6)OF5 octahedra, corners with two equivalent Ca(1)O2F4 octahedra, and  an edgeedge with one Mn(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 32-79°. The Mn(2)-O(1) bond length is 1.91 Å. The Mn(2)-O(2) bond length is 1.92 Å. The Mn(2)-O(3) bond length is 1.82 Å. The Mn(2)-F(6) bond length is 2.14 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 corners with two equivalent Ca(1)O2F4 octahedra, corners with two equivalent Mn(4)O2F4 octahedra, corners with two equivalent Mn(6)OF5 octahedra, and  a cornercorner with one Mn(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 30-65°. The Mn(3)-O(3) bond length is 1.89 Å. The Mn(3)-O(4) bond length is 1.90 Å. The Mn(3)-F(1) bond length is 2.11 Å. The Mn(3)-F(3) bond length is 2.24 Å. The Mn(3)-F(4) bond length is 2.19 Å. The Mn(3)-F(7) bond length is 2.13 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(6), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra,  a cornercorner with one Mn(2)O3F tetrahedra,  an edgeedge with one Mn(6)OF5 octahedra, edges with two equivalent Ca(1)O2F4 octahedra, and  an edgeedge with one Mn(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 30-54°. The Mn(4)-O(1) bond length is 2.12 Å. The Mn(4)-O(2) bond length is 2.23 Å. The Mn(4)-F(1) bond length is 2.17 Å. The Mn(4)-F(4) bond length is 2.20 Å. The Mn(4)-F(6) bond length is 2.17 Å. The Mn(4)-F(8) bond length is 2.19 Å. In the fifth Mn site, Mn(5) is bonded in a 5-coordinate geometry to one O(4), one F(1), one F(2), one F(6), and one F(7) atom. The Mn(5)-O(4) bond length is 1.99 Å. The Mn(5)-F(1) bond length is 2.35 Å. The Mn(5)-F(2) bond length is 2.12 Å. The Mn(5)-F(6) bond length is 2.09 Å. The Mn(5)-F(7) bond length is 2.23 Å. In the sixth Mn site, Mn(6) is bonded to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form MnOF5 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra,  a cornercorner with one Mn(2)O3F tetrahedra,  an edgeedge with one Mn(4)O2F4 octahedra, and edges with two equivalent Ca(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Mn(6)-O(1) bond length is 2.14 Å. The Mn(6)-F(2) bond length is 2.10 Å. The Mn(6)-F(3) bond length is 2.19 Å. The Mn(6)-F(5) bond length is 2.37 Å. The Mn(6)-F(7) bond length is 2.14 Å. The Mn(6)-F(8) bond length is 2.16 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Mn(2), one Mn(4), and one Mn(6) atom to form OCaMn3 trigonal pyramids that share  a cornercorner with one F(8)CaMn3 trigonal pyramid and  an edgeedge with one F(8)CaMn3 trigonal pyramid. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Ca(1), one Mn(1), one Mn(2), and one Mn(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(2) and one Mn(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar 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 T-shaped geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ca(1), 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 Ca(1), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one Mn(1), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(4), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded to one Ca(1), one Mn(1), one Mn(4), and one Mn(6) atom to form distorted FCaMn3 trigonal pyramids that share  a cornercorner with one O(1)CaMn3 trigonal pyramid and  an edgeedge with one O(1)CaMn3 trigonal pyramid.