Na2VCuF7 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 Na(2)F7 hexagonal pyramids, corners with two equivalent V(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 V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 63-69°. In the second Na site, Na(2) is bonded to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form distorted NaF7 hexagonal pyramids that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent V(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(1)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-73°. V(1) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form VF6 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 42-63°. 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(2)F7 hexagonal pyramids, corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and edges with two equivalent Na(2)F7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 40-69°. There are five inequivalent F sites. In the first F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one Cu(1) atom. In the second F site, F(1) is bonded in a 3-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 V(1) atom. In the fourth F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form corner-sharing FNa3V tetrahedra. In the fifth F site, F(4) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one Cu(1) atom.
Na2VCuF7 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 Na(2)F7 hexagonal pyramids, corners with two equivalent V(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 V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 63-69°. Both Na(1)-F(2) bond lengths are 2.58 Å. Both Na(1)-F(3) bond lengths are 2.43 Å. Both Na(1)-F(5) bond lengths are 2.50 Å. In the second Na site, Na(2) is bonded to one F(1), one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form distorted NaF7 hexagonal pyramids that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent V(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, edges with two equivalent Na(1)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-73°. The Na(2)-F(1) bond length is 2.63 Å. The Na(2)-F(2) bond length is 2.26 Å. The Na(2)-F(3) bond length is 2.25 Å. Both Na(2)-F(4) bond lengths are 2.42 Å. Both Na(2)-F(5) bond lengths are 2.69 Å. V(1) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form VF6 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 42-63°. The V(1)-F(2) bond length is 1.99 Å. The V(1)-F(3) bond length is 2.00 Å. Both V(1)-F(4) bond lengths are 1.96 Å. Both V(1)-F(5) bond lengths are 1.97 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(2)F7 hexagonal pyramids, corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Cu(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and edges with two equivalent Na(2)F7 hexagonal pyramids. The corner-sharing octahedral tilt angles range from 40-69°. Both Cu(1)-F(1) bond lengths are 1.94 Å. Both Cu(1)-F(4) bond lengths are 2.03 Å. Both Cu(1)-F(5) bond lengths are 2.13 Å. There are five inequivalent F sites. In the first F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one Cu(1) atom. In the second F site, F(1) is bonded in a 3-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 V(1) atom. In the fourth F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form corner-sharing FNa3V tetrahedra. In the fifth F site, F(4) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one Cu(1) atom.