CaCo6(OF5)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one F(5), two equivalent F(10), and two equivalent F(3) atoms to form distorted CaOF5 octahedra that share  a cornercorner with one Co(4)O2F4 octahedra, corners with four equivalent Ca(1)OF5 octahedra,  a cornercorner with one Co(5)OF4 square pyramid,  a cornercorner with one Co(3)F4 tetrahedra, corners with two equivalent Co(6)OF4 trigonal bipyramids, and  a faceface with one Co(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-11°. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one F(1), one F(2), one F(4), one F(8), and one F(9) atom to form CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra, corners with four equivalent Co(5)OF4 square pyramids, and  an edgeedge with one Co(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-54°. In the second Co site, Co(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one F(1), one F(7), and one F(8) atom. In the third Co site, Co(3) is bonded to one F(2), one F(5), one F(6), and one F(9) atom to form CoF4 tetrahedra that share  a cornercorner with one Ca(1)OF5 octahedra, corners with three equivalent Co(5)OF4 square pyramids,  a cornercorner with one Co(6)OF4 trigonal bipyramid, and  an edgeedge with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles are 73°. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(7), and one F(8) atom to form CoO2F4 octahedra that share  a cornercorner with one Ca(1)OF5 octahedra, corners with four equivalent Co(1)OF5 octahedra,  an edgeedge with one Co(5)OF4 square pyramid, and  an edgeedge with one Co(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-54°. In the fifth Co site, Co(5) is bonded to one O(2), one F(2), one F(4), one F(5), and one F(9) atom to form CoOF4 square pyramids that share  a cornercorner with one Ca(1)OF5 octahedra, corners with four equivalent Co(1)OF5 octahedra, corners with three equivalent Co(3)F4 tetrahedra, and  an edgeedge with one Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-61°. In the sixth Co site, Co(6) is bonded to one O(1), one F(10), one F(3), one F(6), and one F(7) atom to form distorted CoOF4 trigonal bipyramids that share corners with two equivalent Ca(1)OF5 octahedra,  a cornercorner with one Co(3)F4 tetrahedra,  an edgeedge with one Co(4)O2F4 octahedra, and  a faceface with one Ca(1)OF5 octahedra. The corner-sharing octahedral tilt angles are 66°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Co(1), one Co(4), and one Co(5) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Co(1), one Co(2), and one Co(4) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Co(1), one Co(3), and one Co(5) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Co(6) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Co(1), one Co(4), and one Co(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Co(3), and one Co(5) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Co(3) and one Co(6) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one Co(5) atom. In the tenth F site, F(10) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Co(6) atom.
CaCo6(OF5)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(1), one F(5), two equivalent F(10), and two equivalent F(3) atoms to form distorted CaOF5 octahedra that share  a cornercorner with one Co(4)O2F4 octahedra, corners with four equivalent Ca(1)OF5 octahedra,  a cornercorner with one Co(5)OF4 square pyramid,  a cornercorner with one Co(3)F4 tetrahedra, corners with two equivalent Co(6)OF4 trigonal bipyramids, and  a faceface with one Co(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-11°. The Ca(1)-O(1) bond length is 2.40 Å. The Ca(1)-F(5) bond length is 2.31 Å. There is one shorter (2.29 Å) and one longer (2.51 Å) Ca(1)-F(10) bond length. There is one shorter (2.29 Å) and one longer (2.52 Å) Ca(1)-F(3) bond length. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one F(1), one F(2), one F(4), one F(8), and one F(9) atom to form CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra, corners with four equivalent Co(5)OF4 square pyramids, and  an edgeedge with one Co(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-54°. The Co(1)-O(2) bond length is 1.87 Å. The Co(1)-F(1) bond length is 2.17 Å. The Co(1)-F(2) bond length is 2.26 Å. The Co(1)-F(4) bond length is 1.97 Å. The Co(1)-F(8) bond length is 2.17 Å. The Co(1)-F(9) bond length is 2.26 Å. In the second Co site, Co(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one F(1), one F(7), and one F(8) atom. The Co(2)-O(1) bond length is 1.86 Å. The Co(2)-F(1) bond length is 1.95 Å. The Co(2)-F(7) bond length is 2.09 Å. The Co(2)-F(8) bond length is 1.95 Å. In the third Co site, Co(3) is bonded to one F(2), one F(5), one F(6), and one F(9) atom to form CoF4 tetrahedra that share  a cornercorner with one Ca(1)OF5 octahedra, corners with three equivalent Co(5)OF4 square pyramids,  a cornercorner with one Co(6)OF4 trigonal bipyramid, and  an edgeedge with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles are 73°. The Co(3)-F(2) bond length is 1.94 Å. The Co(3)-F(5) bond length is 1.96 Å. The Co(3)-F(6) bond length is 1.90 Å. The Co(3)-F(9) bond length is 1.94 Å. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(7), and one F(8) atom to form CoO2F4 octahedra that share  a cornercorner with one Ca(1)OF5 octahedra, corners with four equivalent Co(1)OF5 octahedra,  an edgeedge with one Co(5)OF4 square pyramid, and  an edgeedge with one Co(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-54°. The Co(4)-O(1) bond length is 2.12 Å. The Co(4)-O(2) bond length is 1.95 Å. The Co(4)-F(1) bond length is 2.05 Å. The Co(4)-F(4) bond length is 2.41 Å. The Co(4)-F(7) bond length is 2.38 Å. The Co(4)-F(8) bond length is 2.05 Å. In the fifth Co site, Co(5) is bonded to one O(2), one F(2), one F(4), one F(5), and one F(9) atom to form CoOF4 square pyramids that share  a cornercorner with one Ca(1)OF5 octahedra, corners with four equivalent Co(1)OF5 octahedra, corners with three equivalent Co(3)F4 tetrahedra, and  an edgeedge with one Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-61°. The Co(5)-O(2) bond length is 1.86 Å. The Co(5)-F(2) bond length is 2.09 Å. The Co(5)-F(4) bond length is 2.03 Å. The Co(5)-F(5) bond length is 2.23 Å. The Co(5)-F(9) bond length is 2.09 Å. In the sixth Co site, Co(6) is bonded to one O(1), one F(10), one F(3), one F(6), and one F(7) atom to form distorted CoOF4 trigonal bipyramids that share corners with two equivalent Ca(1)OF5 octahedra,  a cornercorner with one Co(3)F4 tetrahedra,  an edgeedge with one Co(4)O2F4 octahedra, and  a faceface with one Ca(1)OF5 octahedra. The corner-sharing octahedral tilt angles are 66°. The Co(6)-O(1) bond length is 2.15 Å. The Co(6)-F(10) bond length is 2.04 Å. The Co(6)-F(3) bond length is 2.05 Å. The Co(6)-F(6) bond length is 2.04 Å. The Co(6)-F(7) bond length is 1.92 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Co(1), one Co(4), and one Co(5) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Co(1), one Co(2), and one Co(4) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Co(1), one Co(3), and one Co(5) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Co(6) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Co(1), one Co(4), and one Co(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Co(3), and one Co(5) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Co(3) and one Co(6) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one Co(5) atom. In the tenth F site, F(10) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Co(6) atom.