CaCuF5 crystallizes in the triclinic P-1 space group. Ca(1) is bonded to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form CaF7 pentagonal bipyramids that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 3-41°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 25°. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 25°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one Cu(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Ca(1) and one Cu(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one Cu(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one Cu(2) atom.
CaCuF5 crystallizes in the triclinic P-1 space group. Ca(1) is bonded to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form CaF7 pentagonal bipyramids that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 3-41°. The Ca(1)-F(1) bond length is 2.52 Å. The Ca(1)-F(2) bond length is 2.21 Å. The Ca(1)-F(3) bond length is 2.26 Å. There is one shorter (2.34 Å) and one longer (2.38 Å) Ca(1)-F(4) bond length. There is one shorter (2.33 Å) and one longer (2.37 Å) Ca(1)-F(5) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 25°. Both Cu(1)-F(1) bond lengths are 1.99 Å. Both Cu(1)-F(3) bond lengths are 1.84 Å. Both Cu(1)-F(4) bond lengths are 1.93 Å. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 25°. Both Cu(2)-F(1) bond lengths are 1.96 Å. Both Cu(2)-F(2) bond lengths are 1.87 Å. Both Cu(2)-F(5) bond lengths are 1.95 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one Cu(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Ca(1) and one Cu(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one Cu(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one Cu(2) atom.