CaFe6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form CaF6 octahedra that share  a cornercorner with one Fe(2)OF5 octahedra, corners with two equivalent Fe(6)O2F4 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, edges with two equivalent Fe(5)O2F4 octahedra, and  a faceface with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-67°. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(5), and one F(6) atom to form FeO3F3 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Fe(5)O2F4 octahedra, corners with three equivalent Fe(6)O2F4 octahedra, corners with three equivalent Fe(2)OF5 octahedra, and  an edgeedge with one Fe(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 34-67°. 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 distorted FeOF5 octahedra that share  a cornercorner with one Ca(1)F6 octahedra,  a cornercorner with one Fe(5)O2F4 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, corners with three equivalent Fe(1)O3F3 octahedra,  an edgeedge with one Fe(6)O2F4 octahedra,  a faceface with one Ca(1)F6 octahedra, and  a faceface with one Fe(5)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 40-62°. In the third Fe site, Fe(3) is bonded in a distorted see-saw-like geometry to one O(1), one F(2), one F(3), and one F(6) atom. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(3), one O(4), one F(2), one F(4), and one F(7) atom to form FeO3F3 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Fe(5)O2F4 octahedra, corners with two equivalent Fe(2)OF5 octahedra, corners with three equivalent Fe(6)O2F4 octahedra, and  an edgeedge with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 32-59°. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(2), one F(3), one F(5), one F(7), and one F(8) atom to form FeO2F4 octahedra that share  a cornercorner with one Fe(2)OF5 octahedra, corners with two equivalent Fe(6)O2F4 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, edges with two equivalent Ca(1)F6 octahedra, and  a faceface with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-55°. In the sixth Fe site, Fe(6) is bonded to one O(3), one O(4), one F(3), one F(4), one F(6), and one F(8) atom to form FeO2F4 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Fe(5)O2F4 octahedra, corners with three equivalent Fe(1)O3F3 octahedra, corners with three equivalent Fe(4)O3F3 octahedra, and  an edgeedge with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-55°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(6) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(6) atom. 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(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ca(1), one Fe(3), and one Fe(4) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(3), one Fe(5), and one Fe(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(4), and one Fe(6) atom. In the fifth F site, F(5) is bonded in a distorted trigonal pyramidal geometry to one Ca(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one Fe(6) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(2), one Fe(4), and one Fe(5) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(2), one Fe(5), and one Fe(6) atom.
CaFe6(OF2)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form CaF6 octahedra that share  a cornercorner with one Fe(2)OF5 octahedra, corners with two equivalent Fe(6)O2F4 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, edges with two equivalent Fe(5)O2F4 octahedra, and  a faceface with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-67°. The Ca(1)-F(1) bond length is 2.23 Å. The Ca(1)-F(2) bond length is 2.21 Å. The Ca(1)-F(3) bond length is 2.27 Å. The Ca(1)-F(5) bond length is 2.32 Å. The Ca(1)-F(7) bond length is 2.35 Å. The Ca(1)-F(8) bond length is 2.26 Å. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(5), and one F(6) atom to form FeO3F3 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Fe(5)O2F4 octahedra, corners with three equivalent Fe(6)O2F4 octahedra, corners with three equivalent Fe(2)OF5 octahedra, and  an edgeedge with one Fe(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 34-67°. The Fe(1)-O(2) bond length is 1.97 Å. The Fe(1)-O(3) bond length is 1.97 Å. The Fe(1)-O(4) bond length is 1.98 Å. The Fe(1)-F(1) bond length is 2.19 Å. The Fe(1)-F(5) bond length is 2.23 Å. The Fe(1)-F(6) bond length is 2.02 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 distorted FeOF5 octahedra that share  a cornercorner with one Ca(1)F6 octahedra,  a cornercorner with one Fe(5)O2F4 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, corners with three equivalent Fe(1)O3F3 octahedra,  an edgeedge with one Fe(6)O2F4 octahedra,  a faceface with one Ca(1)F6 octahedra, and  a faceface with one Fe(5)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 40-62°. The Fe(2)-O(2) bond length is 1.94 Å. The Fe(2)-F(1) bond length is 2.03 Å. The Fe(2)-F(4) bond length is 2.04 Å. The Fe(2)-F(5) bond length is 2.22 Å. The Fe(2)-F(7) bond length is 2.54 Å. The Fe(2)-F(8) bond length is 2.09 Å. In the third Fe site, Fe(3) is bonded in a distorted see-saw-like geometry to one O(1), one F(2), one F(3), and one F(6) atom. The Fe(3)-O(1) bond length is 1.90 Å. The Fe(3)-F(2) bond length is 2.01 Å. The Fe(3)-F(3) bond length is 2.09 Å. The Fe(3)-F(6) bond length is 2.03 Å. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(3), one O(4), one F(2), one F(4), and one F(7) atom to form FeO3F3 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Fe(5)O2F4 octahedra, corners with two equivalent Fe(2)OF5 octahedra, corners with three equivalent Fe(6)O2F4 octahedra, and  an edgeedge with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 32-59°. The Fe(4)-O(1) bond length is 1.99 Å. The Fe(4)-O(3) bond length is 1.97 Å. The Fe(4)-O(4) bond length is 1.97 Å. The Fe(4)-F(2) bond length is 2.23 Å. The Fe(4)-F(4) bond length is 2.05 Å. The Fe(4)-F(7) bond length is 2.17 Å. In the fifth Fe site, Fe(5) is bonded to one O(1), one O(2), one F(3), one F(5), one F(7), and one F(8) atom to form FeO2F4 octahedra that share  a cornercorner with one Fe(2)OF5 octahedra, corners with two equivalent Fe(6)O2F4 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, edges with two equivalent Ca(1)F6 octahedra, and  a faceface with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-55°. The Fe(5)-O(1) bond length is 2.00 Å. The Fe(5)-O(2) bond length is 2.00 Å. The Fe(5)-F(3) bond length is 2.22 Å. The Fe(5)-F(5) bond length is 2.30 Å. The Fe(5)-F(7) bond length is 2.29 Å. The Fe(5)-F(8) bond length is 2.30 Å. In the sixth Fe site, Fe(6) is bonded to one O(3), one O(4), one F(3), one F(4), one F(6), and one F(8) atom to form FeO2F4 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Fe(5)O2F4 octahedra, corners with three equivalent Fe(1)O3F3 octahedra, corners with three equivalent Fe(4)O3F3 octahedra, and  an edgeedge with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-55°. The Fe(6)-O(3) bond length is 2.08 Å. The Fe(6)-O(4) bond length is 2.01 Å. The Fe(6)-F(3) bond length is 2.36 Å. The Fe(6)-F(4) bond length is 2.15 Å. The Fe(6)-F(6) bond length is 2.21 Å. The Fe(6)-F(8) bond length is 2.27 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Fe(3), one Fe(4), and one Fe(5) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(6) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(4), and one Fe(6) atom. 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(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ca(1), one Fe(3), and one Fe(4) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(3), one Fe(5), and one Fe(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(2), one Fe(4), and one Fe(6) atom. In the fifth F site, F(5) is bonded in a distorted trigonal pyramidal geometry to one Ca(1), one Fe(1), one Fe(2), and one Fe(5) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one Fe(6) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(2), one Fe(4), and one Fe(5) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Ca(1), one Fe(2), one Fe(5), and one Fe(6) atom.