CaCo6(OF5)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(2), one F(4), one F(8), and one F(9) atom. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded in a 5-coordinate geometry to one O(2), one F(1), one F(2), one F(4), and one F(8) atom. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(10), one F(3), one F(7), and one F(8) atom to form CoOF5 octahedra that share corners with four equivalent Co(6)OF5 octahedra and  an edgeedge with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. In the third Co site, Co(3) is bonded to one F(10), one F(2), one F(3), one F(5), one F(6), and one F(9) atom to form a mixture of corner and edge-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. In the fourth Co site, Co(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(1), one F(7), and one F(8) atom. In the fifth Co site, Co(5) is bonded to one O(2), one F(2), one F(4), one F(5), one F(6), and one F(9) atom to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. In the sixth Co site, Co(6) is bonded to one O(1), one F(10), one F(3), one F(5), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra, and  an edgeedge with one Co(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a distorted tetrahedral geometry to one Ca(1), 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 rectangular see-saw-like geometry to one Ca(1), one Co(1), one Co(2), and one Co(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Co(1), one Co(3), and one Co(5) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Co(2), one Co(3), and one Co(6) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Ca(1), one Co(1), and one Co(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the seventh F site, F(7) is bonded in a 3-coordinate 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 rectangular see-saw-like geometry to one Ca(1), one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Ca(1), one Co(3), and one Co(5) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one Co(6) atom.
CaCo6(OF5)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(2), one F(4), one F(8), and one F(9) atom. The Ca(1)-O(2) bond length is 2.22 Å. The Ca(1)-F(1) bond length is 2.33 Å. The Ca(1)-F(2) bond length is 2.60 Å. The Ca(1)-F(4) bond length is 2.22 Å. The Ca(1)-F(8) bond length is 2.27 Å. The Ca(1)-F(9) bond length is 2.25 Å. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded in a 5-coordinate geometry to one O(2), one F(1), one F(2), one F(4), and one F(8) atom. The Co(1)-O(2) bond length is 1.90 Å. The Co(1)-F(1) bond length is 2.00 Å. The Co(1)-F(2) bond length is 2.09 Å. The Co(1)-F(4) bond length is 1.94 Å. The Co(1)-F(8) bond length is 2.47 Å. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(10), one F(3), one F(7), and one F(8) atom to form CoOF5 octahedra that share corners with four equivalent Co(6)OF5 octahedra and  an edgeedge with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. The Co(2)-O(1) bond length is 1.92 Å. The Co(2)-F(1) bond length is 2.40 Å. The Co(2)-F(10) bond length is 2.10 Å. The Co(2)-F(3) bond length is 2.14 Å. The Co(2)-F(7) bond length is 2.10 Å. The Co(2)-F(8) bond length is 2.16 Å. In the third Co site, Co(3) is bonded to one F(10), one F(2), one F(3), one F(5), one F(6), and one F(9) atom to form a mixture of corner and edge-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. The Co(3)-F(10) bond length is 2.04 Å. The Co(3)-F(2) bond length is 2.43 Å. The Co(3)-F(3) bond length is 2.06 Å. The Co(3)-F(5) bond length is 2.07 Å. The Co(3)-F(6) bond length is 2.07 Å. The Co(3)-F(9) bond length is 2.09 Å. In the fourth Co site, Co(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(1), one F(7), and one F(8) atom. The Co(4)-O(1) bond length is 1.86 Å. The Co(4)-O(2) bond length is 2.02 Å. The Co(4)-F(1) bond length is 2.45 Å. The Co(4)-F(7) bond length is 2.00 Å. The Co(4)-F(8) bond length is 2.08 Å. In the fifth Co site, Co(5) is bonded to one O(2), one F(2), one F(4), one F(5), one F(6), and one F(9) atom to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. The Co(5)-O(2) bond length is 2.06 Å. The Co(5)-F(2) bond length is 2.14 Å. The Co(5)-F(4) bond length is 2.15 Å. The Co(5)-F(5) bond length is 2.01 Å. The Co(5)-F(6) bond length is 2.03 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(5), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra, and  an edgeedge with one Co(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. The Co(6)-O(1) bond length is 1.95 Å. The Co(6)-F(10) bond length is 2.32 Å. The Co(6)-F(3) bond length is 2.21 Å. The Co(6)-F(5) bond length is 2.11 Å. The Co(6)-F(6) bond length is 2.11 Å. The Co(6)-F(7) bond length is 2.20 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a distorted tetrahedral geometry to one Ca(1), 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 rectangular see-saw-like geometry to one Ca(1), one Co(1), one Co(2), and one Co(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Co(1), one Co(3), and one Co(5) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Co(2), one Co(3), and one Co(6) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Ca(1), one Co(1), and one Co(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the seventh F site, F(7) is bonded in a 3-coordinate 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 rectangular see-saw-like geometry to one Ca(1), one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Ca(1), one Co(3), and one Co(5) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one Co(6) atom.