NaCrF6 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(4), two equivalent F(3), and four equivalent F(1) atoms to form distorted NaF7 pentagonal bipyramids that share corners with five equivalent Cr(1)F6 octahedra,  an edgeedge with one Cr(1)F6 octahedra, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 21-39°. Cr(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form CrF6 octahedra that share corners with five equivalent Na(1)F7 pentagonal bipyramids and  an edgeedge with one Na(1)F7 pentagonal bipyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one Cr(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one Cr(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Na(1) and one Cr(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one Cr(1) atom.
NaCrF6 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(4), two equivalent F(3), and four equivalent F(1) atoms to form distorted NaF7 pentagonal bipyramids that share corners with five equivalent Cr(1)F6 octahedra,  an edgeedge with one Cr(1)F6 octahedra, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 21-39°. The Na(1)-F(4) bond length is 2.31 Å. Both Na(1)-F(3) bond lengths are 2.27 Å. There are two shorter (2.28 Å) and two longer (2.44 Å) Na(1)-F(1) bond lengths. Cr(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form CrF6 octahedra that share corners with five equivalent Na(1)F7 pentagonal bipyramids and  an edgeedge with one Na(1)F7 pentagonal bipyramid. The Cr(1)-F(2) bond length is 1.72 Å. The Cr(1)-F(4) bond length is 1.77 Å. Both Cr(1)-F(1) bond lengths are 1.81 Å. Both Cr(1)-F(3) bond lengths are 1.77 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one Cr(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one Cr(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Na(1) and one Cr(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one Cr(1) atom.