Na2NiGaF7 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 Ga(1)F6 octahedra, edges with two equivalent Ga(1)F6 octahedra, and edges with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 52°. 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 Ga(1)F6 octahedra, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 42-49°. Ga(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form GaF6 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 42°. 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 Ga(1) atom to form a mixture of distorted corner and edge-sharing FNa3Ga tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(1), and one Ga(1) atom.
Na2NiGaF7 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 2.47 Å. All Na(1)-F(3) bond lengths are 2.77 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 Ga(1)F6 octahedra, edges with two equivalent Ga(1)F6 octahedra, and edges with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 52°. Both Na(2)-F(1) bond lengths are 2.80 Å. Both Na(2)-F(2) bond lengths are 2.25 Å. All Na(2)-F(3) bond lengths are 2.54 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 Ga(1)F6 octahedra, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 42-49°. Both Ni(1)-F(1) bond lengths are 1.99 Å. All Ni(1)-F(3) bond lengths are 2.02 Å. Ga(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form GaF6 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 42°. Both Ga(1)-F(2) bond lengths are 1.94 Å. All Ga(1)-F(3) bond lengths are 1.92 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 Ga(1) atom to form a mixture of distorted corner and edge-sharing FNa3Ga tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(1), and one Ga(1) atom.