Cu4OF6 crystallizes in the triclinic P1 space group. There are eight inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 5-coordinate geometry to one O(1), one F(1), one F(10), one F(11), and one F(2) atom. In the second Cu site, Cu(2) is bonded to one O(1), one F(11), one F(12), one F(2), and one F(3) atom to form distorted corner-sharing CuOF4 square pyramids. In the third Cu site, Cu(3) is bonded to one O(1), one F(1), one F(2), one F(4), and one F(5) atom to form corner-sharing CuOF4 trigonal bipyramids. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one O(1), one F(12), one F(4), one F(7), and one F(9) atom. In the fifth Cu site, Cu(5) is bonded in a 3-coordinate geometry to one O(2), one F(3), one F(5), one F(6), one F(8), and one F(9) atom. In the sixth Cu site, Cu(6) is bonded to one O(2), one F(10), one F(5), one F(7), and one F(8) atom to form corner-sharing CuOF4 square pyramids. In the seventh Cu site, Cu(7) is bonded to one O(2), one F(11), one F(6), one F(8), and one F(9) atom to form corner-sharing CuOF4 trigonal bipyramids. In the eighth Cu site, Cu(8) is bonded in a 5-coordinate geometry to one O(2), one F(12), one F(4), one F(7), and one F(9) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal pyramidal geometry to one Cu(1), one Cu(2), one Cu(3), and one Cu(4) atom. In the second O site, O(2) is bonded in a trigonal pyramidal geometry to one Cu(5), one Cu(6), one Cu(7), and one Cu(8) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in an L-shaped geometry to one Cu(1) and one Cu(3) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Cu(2) and one Cu(5) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Cu(3), one Cu(4), and one Cu(8) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Cu(3), one Cu(5), and one Cu(6) atom. In the sixth F site, F(6) is bonded in an L-shaped geometry to one Cu(5) and one Cu(7) atom. In the seventh F site, F(7) is bonded in a trigonal non-coplanar geometry to one Cu(4), one Cu(6), and one Cu(8) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Cu(5), one Cu(6), and one Cu(7) atom. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Cu(4), one Cu(5), one Cu(7), and one Cu(8) atom. In the tenth F site, F(10) is bonded in a bent 120 degrees geometry to one Cu(1) and one Cu(6) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(7) atom. In the twelfth F site, F(12) is bonded in a trigonal non-coplanar geometry to one Cu(2), one Cu(4), and one Cu(8) atom.
Cu4OF6 crystallizes in the triclinic P1 space group. There are eight inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 5-coordinate geometry to one O(1), one F(1), one F(10), one F(11), and one F(2) atom. The Cu(1)-O(1) bond length is 1.90 Å. The Cu(1)-F(1) bond length is 2.08 Å. The Cu(1)-F(10) bond length is 1.88 Å. The Cu(1)-F(11) bond length is 2.18 Å. The Cu(1)-F(2) bond length is 2.28 Å. In the second Cu site, Cu(2) is bonded to one O(1), one F(11), one F(12), one F(2), and one F(3) atom to form distorted corner-sharing CuOF4 square pyramids. The Cu(2)-O(1) bond length is 1.97 Å. The Cu(2)-F(11) bond length is 2.33 Å. The Cu(2)-F(12) bond length is 2.07 Å. The Cu(2)-F(2) bond length is 1.95 Å. The Cu(2)-F(3) bond length is 1.90 Å. In the third Cu site, Cu(3) is bonded to one O(1), one F(1), one F(2), one F(4), and one F(5) atom to form corner-sharing CuOF4 trigonal bipyramids. The Cu(3)-O(1) bond length is 1.92 Å. The Cu(3)-F(1) bond length is 1.96 Å. The Cu(3)-F(2) bond length is 2.09 Å. The Cu(3)-F(4) bond length is 2.05 Å. The Cu(3)-F(5) bond length is 1.90 Å. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one O(1), one F(12), one F(4), one F(7), and one F(9) atom. The Cu(4)-O(1) bond length is 1.95 Å. The Cu(4)-F(12) bond length is 2.09 Å. The Cu(4)-F(4) bond length is 1.93 Å. The Cu(4)-F(7) bond length is 2.00 Å. The Cu(4)-F(9) bond length is 2.35 Å. In the fifth Cu site, Cu(5) is bonded in a 3-coordinate geometry to one O(2), one F(3), one F(5), one F(6), one F(8), and one F(9) atom. The Cu(5)-O(2) bond length is 1.91 Å. The Cu(5)-F(3) bond length is 1.88 Å. The Cu(5)-F(5) bond length is 2.37 Å. The Cu(5)-F(6) bond length is 2.05 Å. The Cu(5)-F(8) bond length is 2.40 Å. The Cu(5)-F(9) bond length is 2.53 Å. In the sixth Cu site, Cu(6) is bonded to one O(2), one F(10), one F(5), one F(7), and one F(8) atom to form corner-sharing CuOF4 square pyramids. The Cu(6)-O(2) bond length is 1.98 Å. The Cu(6)-F(10) bond length is 1.89 Å. The Cu(6)-F(5) bond length is 2.24 Å. The Cu(6)-F(7) bond length is 2.06 Å. The Cu(6)-F(8) bond length is 1.93 Å. In the seventh Cu site, Cu(7) is bonded to one O(2), one F(11), one F(6), one F(8), and one F(9) atom to form corner-sharing CuOF4 trigonal bipyramids. The Cu(7)-O(2) bond length is 1.92 Å. The Cu(7)-F(11) bond length is 1.90 Å. The Cu(7)-F(6) bond length is 1.96 Å. The Cu(7)-F(8) bond length is 2.05 Å. The Cu(7)-F(9) bond length is 2.08 Å. In the eighth Cu site, Cu(8) is bonded in a 5-coordinate geometry to one O(2), one F(12), one F(4), one F(7), and one F(9) atom. The Cu(8)-O(2) bond length is 1.94 Å. The Cu(8)-F(12) bond length is 2.00 Å. The Cu(8)-F(4) bond length is 2.37 Å. The Cu(8)-F(7) bond length is 2.08 Å. The Cu(8)-F(9) bond length is 1.94 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal pyramidal geometry to one Cu(1), one Cu(2), one Cu(3), and one Cu(4) atom. In the second O site, O(2) is bonded in a trigonal pyramidal geometry to one Cu(5), one Cu(6), one Cu(7), and one Cu(8) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in an L-shaped geometry to one Cu(1) and one Cu(3) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Cu(2) and one Cu(5) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Cu(3), one Cu(4), and one Cu(8) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Cu(3), one Cu(5), and one Cu(6) atom. In the sixth F site, F(6) is bonded in an L-shaped geometry to one Cu(5) and one Cu(7) atom. In the seventh F site, F(7) is bonded in a trigonal non-coplanar geometry to one Cu(4), one Cu(6), and one Cu(8) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Cu(5), one Cu(6), and one Cu(7) atom. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Cu(4), one Cu(5), one Cu(7), and one Cu(8) atom. In the tenth F site, F(10) is bonded in a bent 120 degrees geometry to one Cu(1) and one Cu(6) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one Cu(7) atom. In the twelfth F site, F(12) is bonded in a trigonal non-coplanar geometry to one Cu(2), one Cu(4), and one Cu(8) atom.