Fe4OF6 crystallizes in the triclinic P1 space group. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(10), one F(3), one F(4), one F(7), one F(8), and one F(9) atom to form a mixture of distorted corner and edge-sharing FeOF6 pentagonal bipyramids. In the second Fe site, Fe(2) is bonded to one O(2), one F(10), one F(12), one F(3), one F(4), one F(6), and one F(7) atom to form distorted FeOF6 pentagonal bipyramids that share  a cornercorner with one Fe(5)OF5 octahedra,  a cornercorner with one Fe(8)OF6 pentagonal bipyramid,  an edgeedge with one Fe(5)OF5 octahedra,  an edgeedge with one Fe(8)OF6 pentagonal bipyramid, edges with two equivalent Fe(1)OF6 pentagonal bipyramids, and edges with two equivalent Fe(6)OF6 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 47°. In the third Fe site, Fe(3) is bonded in a 6-coordinate geometry to one O(2), one F(11), one F(3), one F(5), one F(8), and one F(9) atom. In the fourth Fe site, Fe(4) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(12), one F(4), one F(5), and one F(6) atom. In the fifth Fe site, Fe(5) is bonded to one O(2), one F(11), one F(12), one F(2), one F(5), and one F(6) atom to form a mixture of distorted corner and edge-sharing FeOF5 octahedra. In the sixth Fe site, Fe(6) is bonded to one O(1), one F(1), one F(10), one F(12), one F(2), one F(6), and one F(7) atom to form distorted FeOF6 pentagonal bipyramids that share  a cornercorner with one Fe(5)OF5 octahedra,  a cornercorner with one Fe(1)OF6 pentagonal bipyramid,  an edgeedge with one Fe(5)OF5 octahedra,  an edgeedge with one Fe(1)OF6 pentagonal bipyramid, edges with two equivalent Fe(2)OF6 pentagonal bipyramids, and edges with two equivalent Fe(8)OF6 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 66°. In the seventh Fe site, Fe(7) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(11), one F(5), one F(8), and one F(9) atom. In the eighth Fe site, Fe(8) is bonded to one O(2), one F(1), one F(10), one F(2), one F(7), one F(8), and one F(9) atom to form distorted FeOF6 pentagonal bipyramids that share corners with two equivalent Fe(5)OF5 octahedra,  a cornercorner with one Fe(2)OF6 pentagonal bipyramid,  an edgeedge with one Fe(2)OF6 pentagonal bipyramid, edges with two equivalent Fe(1)OF6 pentagonal bipyramids, and edges with two equivalent Fe(6)OF6 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 53-62°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(4), one Fe(6), and one Fe(7) atom to form OFe4 tetrahedra that share corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids,  an edgeedge with one F(11)Fe4 tetrahedra,  an edgeedge with one F(10)Fe4 trigonal pyramid,  an edgeedge with one F(12)Fe4 trigonal pyramid, and  an edgeedge with one F(9)Fe4 trigonal pyramid. In the second O site, O(2) is bonded to one Fe(2), one Fe(3), one Fe(5), and one Fe(8) atom to form OFe4 tetrahedra that share corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one F(5)Fe4 tetrahedra,  an edgeedge with one F(6)Fe4 trigonal pyramid,  an edgeedge with one F(7)Fe4 trigonal pyramid, and  an edgeedge with one F(8)Fe4 trigonal pyramid. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Fe(6), one Fe(7), and one Fe(8) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Fe(5), one Fe(6), and one Fe(8) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(4) atom. In the fifth F site, F(5) is bonded to one Fe(3), one Fe(4), one Fe(5), and one Fe(7) atom to form distorted FFe4 tetrahedra that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(11)Fe4 tetrahedra. In the sixth F site, F(6) is bonded to one Fe(2), one Fe(4), one Fe(5), and one Fe(6) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(12)Fe4 trigonal pyramids. In the seventh F site, F(7) is bonded to one Fe(1), one Fe(2), one Fe(6), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(10)Fe4 trigonal pyramids. In the eighth F site, F(8) is bonded to one Fe(1), one Fe(3), one Fe(7), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(9)Fe4 trigonal pyramids. In the ninth F site, F(9) is bonded to one Fe(1), one Fe(3), one Fe(7), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(8)Fe4 trigonal pyramids. In the tenth F site, F(10) is bonded to one Fe(1), one Fe(2), one Fe(6), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(7)Fe4 trigonal pyramids. In the eleventh F site, F(11) is bonded to one Fe(3), one Fe(4), one Fe(5), and one Fe(7) atom to form distorted FFe4 tetrahedra that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(5)Fe4 tetrahedra. In the twelfth F site, F(12) is bonded to one Fe(2), one Fe(4), one Fe(5), and one Fe(6) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(6)Fe4 trigonal pyramids.
Fe4OF6 crystallizes in the triclinic P1 space group. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one F(10), one F(3), one F(4), one F(7), one F(8), and one F(9) atom to form a mixture of distorted corner and edge-sharing FeOF6 pentagonal bipyramids. The Fe(1)-O(1) bond length is 2.10 Å. The Fe(1)-F(10) bond length is 2.27 Å. The Fe(1)-F(3) bond length is 2.20 Å. The Fe(1)-F(4) bond length is 2.10 Å. The Fe(1)-F(7) bond length is 2.19 Å. The Fe(1)-F(8) bond length is 2.12 Å. The Fe(1)-F(9) bond length is 2.47 Å. In the second Fe site, Fe(2) is bonded to one O(2), one F(10), one F(12), one F(3), one F(4), one F(6), and one F(7) atom to form distorted FeOF6 pentagonal bipyramids that share  a cornercorner with one Fe(5)OF5 octahedra,  a cornercorner with one Fe(8)OF6 pentagonal bipyramid,  an edgeedge with one Fe(5)OF5 octahedra,  an edgeedge with one Fe(8)OF6 pentagonal bipyramid, edges with two equivalent Fe(1)OF6 pentagonal bipyramids, and edges with two equivalent Fe(6)OF6 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 47°. The Fe(2)-O(2) bond length is 2.09 Å. The Fe(2)-F(10) bond length is 2.20 Å. The Fe(2)-F(12) bond length is 2.12 Å. The Fe(2)-F(3) bond length is 2.09 Å. The Fe(2)-F(4) bond length is 2.21 Å. The Fe(2)-F(6) bond length is 2.47 Å. The Fe(2)-F(7) bond length is 2.27 Å. In the third Fe site, Fe(3) is bonded in a 6-coordinate geometry to one O(2), one F(11), one F(3), one F(5), one F(8), and one F(9) atom. The Fe(3)-O(2) bond length is 2.00 Å. The Fe(3)-F(11) bond length is 2.15 Å. The Fe(3)-F(3) bond length is 2.02 Å. The Fe(3)-F(5) bond length is 2.43 Å. The Fe(3)-F(8) bond length is 2.31 Å. The Fe(3)-F(9) bond length is 2.20 Å. In the fourth Fe site, Fe(4) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(12), one F(4), one F(5), and one F(6) atom. The Fe(4)-O(1) bond length is 2.00 Å. The Fe(4)-F(11) bond length is 2.42 Å. The Fe(4)-F(12) bond length is 2.30 Å. The Fe(4)-F(4) bond length is 2.03 Å. The Fe(4)-F(5) bond length is 2.15 Å. The Fe(4)-F(6) bond length is 2.20 Å. In the fifth Fe site, Fe(5) is bonded to one O(2), one F(11), one F(12), one F(2), one F(5), and one F(6) atom to form a mixture of distorted corner and edge-sharing FeOF5 octahedra. The Fe(5)-O(2) bond length is 2.00 Å. The Fe(5)-F(11) bond length is 2.15 Å. The Fe(5)-F(12) bond length is 2.20 Å. The Fe(5)-F(2) bond length is 2.03 Å. The Fe(5)-F(5) bond length is 2.40 Å. The Fe(5)-F(6) bond length is 2.31 Å. In the sixth Fe site, Fe(6) is bonded to one O(1), one F(1), one F(10), one F(12), one F(2), one F(6), and one F(7) atom to form distorted FeOF6 pentagonal bipyramids that share  a cornercorner with one Fe(5)OF5 octahedra,  a cornercorner with one Fe(1)OF6 pentagonal bipyramid,  an edgeedge with one Fe(5)OF5 octahedra,  an edgeedge with one Fe(1)OF6 pentagonal bipyramid, edges with two equivalent Fe(2)OF6 pentagonal bipyramids, and edges with two equivalent Fe(8)OF6 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 66°. The Fe(6)-O(1) bond length is 2.09 Å. The Fe(6)-F(1) bond length is 2.09 Å. The Fe(6)-F(10) bond length is 2.27 Å. The Fe(6)-F(12) bond length is 2.48 Å. The Fe(6)-F(2) bond length is 2.21 Å. The Fe(6)-F(6) bond length is 2.13 Å. The Fe(6)-F(7) bond length is 2.20 Å. In the seventh Fe site, Fe(7) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(11), one F(5), one F(8), and one F(9) atom. The Fe(7)-O(1) bond length is 2.00 Å. The Fe(7)-F(1) bond length is 2.03 Å. The Fe(7)-F(11) bond length is 2.41 Å. The Fe(7)-F(5) bond length is 2.15 Å. The Fe(7)-F(8) bond length is 2.20 Å. The Fe(7)-F(9) bond length is 2.32 Å. In the eighth Fe site, Fe(8) is bonded to one O(2), one F(1), one F(10), one F(2), one F(7), one F(8), and one F(9) atom to form distorted FeOF6 pentagonal bipyramids that share corners with two equivalent Fe(5)OF5 octahedra,  a cornercorner with one Fe(2)OF6 pentagonal bipyramid,  an edgeedge with one Fe(2)OF6 pentagonal bipyramid, edges with two equivalent Fe(1)OF6 pentagonal bipyramids, and edges with two equivalent Fe(6)OF6 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 53-62°. The Fe(8)-O(2) bond length is 2.10 Å. The Fe(8)-F(1) bond length is 2.20 Å. The Fe(8)-F(10) bond length is 2.19 Å. The Fe(8)-F(2) bond length is 2.09 Å. The Fe(8)-F(7) bond length is 2.27 Å. The Fe(8)-F(8) bond length is 2.47 Å. The Fe(8)-F(9) bond length is 2.12 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(4), one Fe(6), and one Fe(7) atom to form OFe4 tetrahedra that share corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids,  an edgeedge with one F(11)Fe4 tetrahedra,  an edgeedge with one F(10)Fe4 trigonal pyramid,  an edgeedge with one F(12)Fe4 trigonal pyramid, and  an edgeedge with one F(9)Fe4 trigonal pyramid. In the second O site, O(2) is bonded to one Fe(2), one Fe(3), one Fe(5), and one Fe(8) atom to form OFe4 tetrahedra that share corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one F(5)Fe4 tetrahedra,  an edgeedge with one F(6)Fe4 trigonal pyramid,  an edgeedge with one F(7)Fe4 trigonal pyramid, and  an edgeedge with one F(8)Fe4 trigonal pyramid. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Fe(6), one Fe(7), and one Fe(8) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Fe(5), one Fe(6), and one Fe(8) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(4) atom. In the fifth F site, F(5) is bonded to one Fe(3), one Fe(4), one Fe(5), and one Fe(7) atom to form distorted FFe4 tetrahedra that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(11)Fe4 tetrahedra. In the sixth F site, F(6) is bonded to one Fe(2), one Fe(4), one Fe(5), and one Fe(6) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(12)Fe4 trigonal pyramids. In the seventh F site, F(7) is bonded to one Fe(1), one Fe(2), one Fe(6), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(10)Fe4 trigonal pyramids. In the eighth F site, F(8) is bonded to one Fe(1), one Fe(3), one Fe(7), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(1)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(2)Fe4 tetrahedra, and edges with two equivalent F(9)Fe4 trigonal pyramids. In the ninth F site, F(9) is bonded to one Fe(1), one Fe(3), one Fe(7), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(8)Fe4 trigonal pyramids. In the tenth F site, F(10) is bonded to one Fe(1), one Fe(2), one Fe(6), and one Fe(8) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(7)Fe4 trigonal pyramids. In the eleventh F site, F(11) is bonded to one Fe(3), one Fe(4), one Fe(5), and one Fe(7) atom to form distorted FFe4 tetrahedra that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(12)Fe4 trigonal pyramids, corners with two equivalent F(6)Fe4 trigonal pyramids, corners with two equivalent F(8)Fe4 trigonal pyramids, corners with two equivalent F(9)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(5)Fe4 tetrahedra. In the twelfth F site, F(12) is bonded to one Fe(2), one Fe(4), one Fe(5), and one Fe(6) atom to form distorted FFe4 trigonal pyramids that share corners with two equivalent O(2)Fe4 tetrahedra, corners with two equivalent F(11)Fe4 tetrahedra, corners with two equivalent F(5)Fe4 tetrahedra, corners with two equivalent F(10)Fe4 trigonal pyramids, corners with two equivalent F(7)Fe4 trigonal pyramids,  an edgeedge with one O(1)Fe4 tetrahedra, and edges with two equivalent F(6)Fe4 trigonal pyramids.