CaFe6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one F(1), one F(4), one F(6), and one F(8) atom. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one F(5), and one F(8) atom. In the second Fe site, Fe(2) is bonded to one O(2), one F(1), one F(4), one F(5), one F(7), and one F(8) atom to form FeOF5 octahedra that share corners with three equivalent Fe(5)O2F4 octahedra,  a cornercorner with one Fe(6)O2F3 square pyramid,  a cornercorner with one Fe(4)O3F2 trigonal bipyramid, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 31-60°. In the third Fe site, Fe(3) is bonded to one O(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form FeOF5 octahedra that share corners with three equivalent Fe(5)O2F4 octahedra, corners with three equivalent Fe(4)O3F2 trigonal bipyramids,  an edgeedge with one Fe(2)OF5 octahedra, and  an edgeedge with one Fe(6)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 44-58°. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(3), one O(4), one F(2), and one F(7) atom to form distorted FeO3F2 trigonal bipyramids that share  a cornercorner with one Fe(2)OF5 octahedra, corners with three equivalent Fe(3)OF5 octahedra, corners with two equivalent Fe(6)O2F3 square pyramids, and  an edgeedge with one Fe(5)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(8) atom to form FeO2F4 octahedra that share corners with three equivalent Fe(2)OF5 octahedra, corners with three equivalent Fe(3)OF5 octahedra,  a cornercorner with one Fe(6)O2F3 square pyramid, and  an edgeedge with one Fe(4)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-60°. In the sixth Fe site, Fe(6) is bonded to one O(3), one O(4), one F(3), one F(4), and one F(6) atom to form FeO2F3 square pyramids that share  a cornercorner with one Fe(5)O2F4 octahedra,  a cornercorner with one Fe(2)OF5 octahedra, corners with two equivalent Fe(4)O3F2 trigonal bipyramids, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-78°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the third O site, O(3) is bonded to one Ca(1), one Fe(1), one Fe(4), and one Fe(6) atom to form a mixture of distorted edge and corner-sharing OCaFe3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Ca(1), one Fe(1), one Fe(4), and one Fe(6) atom to form a mixture of distorted edge and corner-sharing OCaFe3 trigonal pyramids. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Ca(1), one Fe(2), and one Fe(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Fe(3), one Fe(5), and one Fe(6) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Ca(1), one Fe(2), and one Fe(6) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Fe(3), and one Fe(6) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(1), one Fe(2), and one Fe(5) atom.
CaFe6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one F(1), one F(4), one F(6), and one F(8) atom. The Ca(1)-O(2) bond length is 2.53 Å. The Ca(1)-O(3) bond length is 2.38 Å. The Ca(1)-O(4) bond length is 2.38 Å. The Ca(1)-F(1) bond length is 2.40 Å. The Ca(1)-F(4) bond length is 2.33 Å. The Ca(1)-F(6) bond length is 2.19 Å. The Ca(1)-F(8) bond length is 2.43 Å. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one F(5), and one F(8) atom. The Fe(1)-O(2) bond length is 2.06 Å. The Fe(1)-O(3) bond length is 2.04 Å. The Fe(1)-O(4) bond length is 2.10 Å. The Fe(1)-F(5) bond length is 1.99 Å. The Fe(1)-F(8) bond length is 2.63 Å. In the second Fe site, Fe(2) is bonded to one O(2), one F(1), one F(4), one F(5), one F(7), and one F(8) atom to form FeOF5 octahedra that share corners with three equivalent Fe(5)O2F4 octahedra,  a cornercorner with one Fe(6)O2F3 square pyramid,  a cornercorner with one Fe(4)O3F2 trigonal bipyramid, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 31-60°. The Fe(2)-O(2) bond length is 2.00 Å. The Fe(2)-F(1) bond length is 2.06 Å. The Fe(2)-F(4) bond length is 2.20 Å. The Fe(2)-F(5) bond length is 2.19 Å. The Fe(2)-F(7) bond length is 2.19 Å. The Fe(2)-F(8) bond length is 2.26 Å. In the third Fe site, Fe(3) is bonded to one O(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form FeOF5 octahedra that share corners with three equivalent Fe(5)O2F4 octahedra, corners with three equivalent Fe(4)O3F2 trigonal bipyramids,  an edgeedge with one Fe(2)OF5 octahedra, and  an edgeedge with one Fe(6)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 44-58°. The Fe(3)-O(1) bond length is 2.02 Å. The Fe(3)-F(2) bond length is 2.11 Å. The Fe(3)-F(3) bond length is 2.23 Å. The Fe(3)-F(5) bond length is 2.10 Å. The Fe(3)-F(6) bond length is 2.06 Å. The Fe(3)-F(7) bond length is 2.22 Å. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(3), one O(4), one F(2), and one F(7) atom to form distorted FeO3F2 trigonal bipyramids that share  a cornercorner with one Fe(2)OF5 octahedra, corners with three equivalent Fe(3)OF5 octahedra, corners with two equivalent Fe(6)O2F3 square pyramids, and  an edgeedge with one Fe(5)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The Fe(4)-O(1) bond length is 1.98 Å. The Fe(4)-O(3) bond length is 1.95 Å. The Fe(4)-O(4) bond length is 1.97 Å. The Fe(4)-F(2) bond length is 2.16 Å. The Fe(4)-F(7) bond length is 1.97 Å. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(8) atom to form FeO2F4 octahedra that share corners with three equivalent Fe(2)OF5 octahedra, corners with three equivalent Fe(3)OF5 octahedra,  a cornercorner with one Fe(6)O2F3 square pyramid, and  an edgeedge with one Fe(4)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-60°. The Fe(5)-O(1) bond length is 1.90 Å. The Fe(5)-O(2) bond length is 1.94 Å. The Fe(5)-F(1) bond length is 2.06 Å. The Fe(5)-F(2) bond length is 2.14 Å. The Fe(5)-F(3) bond length is 2.04 Å. The Fe(5)-F(8) bond length is 2.17 Å. In the sixth Fe site, Fe(6) is bonded to one O(3), one O(4), one F(3), one F(4), and one F(6) atom to form FeO2F3 square pyramids that share  a cornercorner with one Fe(5)O2F4 octahedra,  a cornercorner with one Fe(2)OF5 octahedra, corners with two equivalent Fe(4)O3F2 trigonal bipyramids, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-78°. The Fe(6)-O(3) bond length is 2.07 Å. The Fe(6)-O(4) bond length is 2.04 Å. The Fe(6)-F(3) bond length is 2.14 Å. The Fe(6)-F(4) bond length is 2.09 Å. The Fe(6)-F(6) bond length is 2.14 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the third O site, O(3) is bonded to one Ca(1), one Fe(1), one Fe(4), and one Fe(6) atom to form a mixture of distorted edge and corner-sharing OCaFe3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Ca(1), one Fe(1), one Fe(4), and one Fe(6) atom to form a mixture of distorted edge and corner-sharing OCaFe3 trigonal pyramids. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Ca(1), one Fe(2), and one Fe(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Fe(3), one Fe(5), and one Fe(6) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Ca(1), one Fe(2), and one Fe(6) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Fe(3), and one Fe(6) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(3), and one Fe(4) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(1), one Fe(2), and one Fe(5) atom.