Na2ScCuF7 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(1), two equivalent F(4), and two equivalent F(5) atoms to form NaF6 octahedra that share corners with two equivalent Na(2)F7 hexagonal pyramids, corners with two equivalent Sc(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(2)F7 hexagonal pyramids, edges with two equivalent Na(1)F6 octahedra, and edges with two equivalent Sc(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 61-68°. In the second Na site, Na(2) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form NaF7 hexagonal pyramids that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Sc(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(1)F6 octahedra, edges with two equivalent Sc(1)F6 octahedra, and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-71°. Sc(1) is bonded to one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form ScF6 octahedra that share corners with two equivalent Na(2)F7 hexagonal pyramids, corners with two equivalent Na(1)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra, edges with two equivalent Na(2)F7 hexagonal pyramids, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-61°. Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CuF6 octahedra that share corners with two equivalent Na(2)F7 hexagonal pyramids, corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Sc(1)F6 octahedra, and edges with two equivalent Na(2)F7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 35-68°. There are five inequivalent F sites. In the first F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2) and two equivalent Cu(1) atoms. In the second F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Sc(1) atom. In the third F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one Sc(1) atom to form FNa3Sc tetrahedra that share corners with two equivalent F(5)Na3Sc tetrahedra, corners with four equivalent F(1)Na2ScCu tetrahedra, and edges with two equivalent F(1)Na2ScCu tetrahedra. In the fourth F site, F(1) is bonded to one Na(1), one Na(2), one Sc(1), and one Cu(1) atom to form distorted FNa2ScCu tetrahedra that share corners with two equivalent F(5)Na3Sc tetrahedra, corners with four equivalent F(1)Na2ScCu tetrahedra, and  an edgeedge with one F(5)Na3Sc tetrahedra. In the fifth F site, F(2) is bonded in a 3-coordinate geometry to one Na(2), one Sc(1), and one Cu(1) atom.
Na2ScCuF7 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(1), two equivalent F(4), and two equivalent F(5) atoms to form NaF6 octahedra that share corners with two equivalent Na(2)F7 hexagonal pyramids, corners with two equivalent Sc(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(2)F7 hexagonal pyramids, edges with two equivalent Na(1)F6 octahedra, and edges with two equivalent Sc(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 61-68°. Both Na(1)-F(1) bond lengths are 2.44 Å. Both Na(1)-F(4) bond lengths are 2.62 Å. Both Na(1)-F(5) bond lengths are 2.40 Å. In the second Na site, Na(2) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form NaF7 hexagonal pyramids that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Sc(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(1)F6 octahedra, edges with two equivalent Sc(1)F6 octahedra, and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-71°. The Na(2)-F(3) bond length is 2.48 Å. The Na(2)-F(4) bond length is 2.29 Å. The Na(2)-F(5) bond length is 2.30 Å. Both Na(2)-F(1) bond lengths are 2.57 Å. Both Na(2)-F(2) bond lengths are 2.51 Å. Sc(1) is bonded to one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form ScF6 octahedra that share corners with two equivalent Na(2)F7 hexagonal pyramids, corners with two equivalent Na(1)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra, edges with two equivalent Na(2)F7 hexagonal pyramids, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-61°. The Sc(1)-F(4) bond length is 2.03 Å. The Sc(1)-F(5) bond length is 2.08 Å. Both Sc(1)-F(1) bond lengths are 2.02 Å. Both Sc(1)-F(2) bond lengths are 2.05 Å. Cu(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CuF6 octahedra that share corners with two equivalent Na(2)F7 hexagonal pyramids, corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent Sc(1)F6 octahedra, and edges with two equivalent Na(2)F7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 35-68°. Both Cu(1)-F(1) bond lengths are 2.25 Å. Both Cu(1)-F(2) bond lengths are 1.93 Å. Both Cu(1)-F(3) bond lengths are 1.94 Å. There are five inequivalent F sites. In the first F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2) and two equivalent Cu(1) atoms. In the second F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Sc(1) atom. In the third F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one Sc(1) atom to form FNa3Sc tetrahedra that share corners with two equivalent F(5)Na3Sc tetrahedra, corners with four equivalent F(1)Na2ScCu tetrahedra, and edges with two equivalent F(1)Na2ScCu tetrahedra. In the fourth F site, F(1) is bonded to one Na(1), one Na(2), one Sc(1), and one Cu(1) atom to form distorted FNa2ScCu tetrahedra that share corners with two equivalent F(5)Na3Sc tetrahedra, corners with four equivalent F(1)Na2ScCu tetrahedra, and  an edgeedge with one F(5)Na3Sc tetrahedra. In the fifth F site, F(2) is bonded in a 3-coordinate geometry to one Na(2), one Sc(1), and one Cu(1) atom.