Na3CrF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent F(1), two equivalent F(3), and three equivalent F(2) atoms. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with six equivalent Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. Cr(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CrF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one Cr(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(1), and one Cr(1) atom. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Cr(1) atom to form distorted corner-sharing FNa3Cr tetrahedra.
Na3CrF6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent F(1), two equivalent F(3), and three equivalent F(2) atoms. There is one shorter (2.29 Å) and one longer (2.49 Å) Na(1)-F(1) bond length. There is one shorter (2.26 Å) and one longer (2.31 Å) Na(1)-F(3) bond length. There are a spread of Na(1)-F(2) bond distances ranging from 2.28-2.70 Å. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with six equivalent Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. Both Na(2)-F(1) bond lengths are 2.26 Å. Both Na(2)-F(2) bond lengths are 2.19 Å. Both Na(2)-F(3) bond lengths are 2.25 Å. Cr(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CrF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. Both Cr(1)-F(1) bond lengths are 1.92 Å. Both Cr(1)-F(2) bond lengths are 1.91 Å. Both Cr(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 4-coordinate geometry to one Na(2), two equivalent Na(1), and one Cr(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(1), and one Cr(1) atom. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Cr(1) atom to form distorted corner-sharing FNa3Cr tetrahedra.