Na2NiInF7 crystallizes in the orthorhombic Pnma 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 two equivalent F(1), two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms. 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 distorted NaF7 pentagonal bipyramids that share corners with two equivalent Ni(1)F6 octahedra,  a cornercorner with one In(1)F7 pentagonal bipyramid, edges with two equivalent Ni(1)F6 octahedra, and edges with three equivalent In(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 56°. Ni(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra, corners with two equivalent Na(2)F7 pentagonal bipyramids, corners with two equivalent In(1)F7 pentagonal bipyramids, edges with two equivalent Na(2)F7 pentagonal bipyramids, and edges with two equivalent In(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 43°. In(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted InF7 pentagonal bipyramids that share corners with two equivalent Ni(1)F6 octahedra,  a cornercorner with one Na(2)F7 pentagonal bipyramid, edges with two equivalent Ni(1)F6 octahedra, and edges with three equivalent Na(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 39°. There are five inequivalent F sites. In the first F site, F(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Ni(1), and one In(1) atom. In the second F site, F(4) is bonded to one Na(2), two equivalent Na(1), and one In(1) atom to form FNa3In tetrahedra that share corners with two equivalent F(4)Na3In tetrahedra, corners with four equivalent F(1)Na2InNi tetrahedra, corners with four equivalent F(5)Na3In tetrahedra,  an edgeedge with one F(5)Na3In tetrahedra, and edges with two equivalent F(1)Na2InNi tetrahedra. In the third F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one In(1) atom to form FNa3In tetrahedra that share corners with two equivalent F(5)Na3In tetrahedra, corners with four equivalent F(1)Na2InNi tetrahedra, corners with four equivalent F(4)Na3In tetrahedra,  an edgeedge with one F(4)Na3In tetrahedra, and edges with two equivalent F(1)Na2InNi tetrahedra. In the fourth F site, F(1) is bonded to one Na(1), one Na(2), one Ni(1), and one In(1) atom to form distorted FNa2InNi tetrahedra that share corners with two equivalent F(4)Na3In tetrahedra, corners with two equivalent F(5)Na3In tetrahedra, corners with four equivalent F(1)Na2InNi tetrahedra,  an edgeedge with one F(4)Na3In tetrahedra, and  an edgeedge with one F(5)Na3In tetrahedra. In the fifth F site, F(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(1), and one In(1) atom.
Na2NiInF7 crystallizes in the orthorhombic Pnma 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 two equivalent F(1), two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms. Both Na(1)-F(1) bond lengths are 2.68 Å. Both Na(1)-F(2) bond lengths are 2.72 Å. Both Na(1)-F(4) bond lengths are 2.45 Å. Both Na(1)-F(5) bond lengths are 2.37 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 distorted NaF7 pentagonal bipyramids that share corners with two equivalent Ni(1)F6 octahedra,  a cornercorner with one In(1)F7 pentagonal bipyramid, edges with two equivalent Ni(1)F6 octahedra, and edges with three equivalent In(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 56°. The Na(2)-F(3) bond length is 2.43 Å. The Na(2)-F(4) bond length is 2.25 Å. The Na(2)-F(5) bond length is 2.31 Å. Both Na(2)-F(1) bond lengths are 2.35 Å. Both Na(2)-F(2) bond lengths are 2.52 Å. Ni(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra, corners with two equivalent Na(2)F7 pentagonal bipyramids, corners with two equivalent In(1)F7 pentagonal bipyramids, edges with two equivalent Na(2)F7 pentagonal bipyramids, and edges with two equivalent In(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 43°. Both Ni(1)-F(1) bond lengths are 2.03 Å. Both Ni(1)-F(2) bond lengths are 2.02 Å. Both Ni(1)-F(3) bond lengths are 2.00 Å. In(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted InF7 pentagonal bipyramids that share corners with two equivalent Ni(1)F6 octahedra,  a cornercorner with one Na(2)F7 pentagonal bipyramid, edges with two equivalent Ni(1)F6 octahedra, and edges with three equivalent Na(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 39°. The In(1)-F(3) bond length is 2.52 Å. The In(1)-F(4) bond length is 2.09 Å. The In(1)-F(5) bond length is 2.11 Å. Both In(1)-F(1) bond lengths are 2.18 Å. Both In(1)-F(2) bond lengths are 2.16 Å. There are five inequivalent F sites. In the first F site, F(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Ni(1), and one In(1) atom. In the second F site, F(4) is bonded to one Na(2), two equivalent Na(1), and one In(1) atom to form FNa3In tetrahedra that share corners with two equivalent F(4)Na3In tetrahedra, corners with four equivalent F(1)Na2InNi tetrahedra, corners with four equivalent F(5)Na3In tetrahedra,  an edgeedge with one F(5)Na3In tetrahedra, and edges with two equivalent F(1)Na2InNi tetrahedra. In the third F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one In(1) atom to form FNa3In tetrahedra that share corners with two equivalent F(5)Na3In tetrahedra, corners with four equivalent F(1)Na2InNi tetrahedra, corners with four equivalent F(4)Na3In tetrahedra,  an edgeedge with one F(4)Na3In tetrahedra, and edges with two equivalent F(1)Na2InNi tetrahedra. In the fourth F site, F(1) is bonded to one Na(1), one Na(2), one Ni(1), and one In(1) atom to form distorted FNa2InNi tetrahedra that share corners with two equivalent F(4)Na3In tetrahedra, corners with two equivalent F(5)Na3In tetrahedra, corners with four equivalent F(1)Na2InNi tetrahedra,  an edgeedge with one F(4)Na3In tetrahedra, and  an edgeedge with one F(5)Na3In tetrahedra. In the fifth F site, F(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(1), and one In(1) atom.