Na2CuCrF7 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(5) atoms to form distorted NaF6 octahedra that share corners with two equivalent Cr(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(1)F6 octahedra, and edges with two equivalent Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 63-72°. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms. Cr(1) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form CrF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-63°. Cu(1) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, and corners with four equivalent Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-72°. There are five inequivalent F sites. In the first F site, F(5) is bonded to one Na(1), one Na(2), one Cr(1), and one Cu(1) atom to form distorted FNa2CrCu tetrahedra that share corners with two equivalent F(3)Na3Cr tetrahedra, corners with four equivalent F(5)Na2CrCu tetrahedra, and  an edgeedge with one F(3)Na3Cr tetrahedra. In the second F site, F(1) is bonded in a 2-coordinate geometry to one Na(2) and two equivalent Cu(1) atoms. In the third F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Cr(1) atom. In the fourth F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Cr(1) atom to form distorted FNa3Cr tetrahedra that share corners with two equivalent F(3)Na3Cr tetrahedra, corners with four equivalent F(5)Na2CrCu tetrahedra, and edges with two equivalent F(5)Na2CrCu tetrahedra. In the fifth F site, F(4) is bonded in a 3-coordinate geometry to one Na(2), one Cr(1), and one Cu(1) atom.
Na2CuCrF7 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(5) atoms to form distorted NaF6 octahedra that share corners with two equivalent Cr(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(1)F6 octahedra, and edges with two equivalent Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 63-72°. Both Na(1)-F(2) bond lengths are 2.56 Å. Both Na(1)-F(3) bond lengths are 2.43 Å. Both Na(1)-F(5) bond lengths are 2.52 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms. The Na(2)-F(1) bond length is 2.72 Å. The Na(2)-F(2) bond length is 2.28 Å. The Na(2)-F(3) bond length is 2.26 Å. Both Na(2)-F(4) bond lengths are 2.47 Å. Both Na(2)-F(5) bond lengths are 2.55 Å. Cr(1) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form CrF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-63°. The Cr(1)-F(2) bond length is 1.97 Å. The Cr(1)-F(3) bond length is 1.97 Å. Both Cr(1)-F(4) bond lengths are 1.96 Å. Both Cr(1)-F(5) bond lengths are 1.93 Å. Cu(1) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(5) atoms to form CuF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, and corners with four equivalent Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-72°. Both Cu(1)-F(1) bond lengths are 1.94 Å. Both Cu(1)-F(4) bond lengths are 1.95 Å. Both Cu(1)-F(5) bond lengths are 2.20 Å. There are five inequivalent F sites. In the first F site, F(5) is bonded to one Na(1), one Na(2), one Cr(1), and one Cu(1) atom to form distorted FNa2CrCu tetrahedra that share corners with two equivalent F(3)Na3Cr tetrahedra, corners with four equivalent F(5)Na2CrCu tetrahedra, and  an edgeedge with one F(3)Na3Cr tetrahedra. In the second F site, F(1) is bonded in a 2-coordinate geometry to one Na(2) and two equivalent Cu(1) atoms. In the third F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Cr(1) atom. In the fourth F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Cr(1) atom to form distorted FNa3Cr tetrahedra that share corners with two equivalent F(3)Na3Cr tetrahedra, corners with four equivalent F(5)Na2CrCu tetrahedra, and edges with two equivalent F(5)Na2CrCu tetrahedra. In the fifth F site, F(4) is bonded in a 3-coordinate geometry to one Na(2), one Cr(1), and one Cu(1) atom.