Na2VNiF7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted body-centered cubic geometry to four equivalent F(2) and four equivalent F(3) atoms. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and four equivalent F(3) atoms to form distorted NaF8 hexagonal bipyramids that share corners with two equivalent Na(2)F8 hexagonal bipyramids, corners with two equivalent V(1)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 54°. V(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent Na(2)F8 hexagonal bipyramids, corners with four equivalent Ni(1)F6 octahedra, and edges with two equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 43°. Ni(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-45°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to two equivalent Na(2) and two equivalent Ni(1) atoms. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FNa3V tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one Ni(1) atom.
Na2VNiF7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted body-centered cubic geometry to four equivalent F(2) and four equivalent F(3) atoms. All Na(1)-F(2) bond lengths are 2.48 Å. All Na(1)-F(3) bond lengths are 2.76 Å. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and four equivalent F(3) atoms to form distorted NaF8 hexagonal bipyramids that share corners with two equivalent Na(2)F8 hexagonal bipyramids, corners with two equivalent V(1)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 54°. Both Na(2)-F(1) bond lengths are 2.85 Å. Both Na(2)-F(2) bond lengths are 2.24 Å. All Na(2)-F(3) bond lengths are 2.55 Å. V(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent Na(2)F8 hexagonal bipyramids, corners with four equivalent Ni(1)F6 octahedra, and edges with two equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 43°. Both V(1)-F(2) bond lengths are 1.99 Å. All V(1)-F(3) bond lengths are 1.98 Å. Ni(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-45°. Both Ni(1)-F(1) bond lengths are 1.98 Å. All Ni(1)-F(3) bond lengths are 2.01 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to two equivalent Na(2) and two equivalent Ni(1) atoms. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FNa3V tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one Ni(1) atom.