Na3BiF6 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to two equivalent F(2) and two equivalent F(3) atoms. In the second Na site, Na(2) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(3) atoms. In the third Na site, Na(3) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(2) atoms. Bi(1) is bonded in an octahedral geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Na(2), one Na(3), and one Bi(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(3), and one Bi(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Bi(1) atom.
Na3BiF6 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to two equivalent F(2) and two equivalent F(3) atoms. Both Na(1)-F(2) bond lengths are 2.20 Å. Both Na(1)-F(3) bond lengths are 2.31 Å. In the second Na site, Na(2) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(3) atoms. Both Na(2)-F(1) bond lengths are 2.21 Å. Both Na(2)-F(3) bond lengths are 2.24 Å. In the third Na site, Na(3) is bonded in a square co-planar geometry to two equivalent F(1) and two equivalent F(2) atoms. Both Na(3)-F(1) bond lengths are 2.24 Å. Both Na(3)-F(2) bond lengths are 2.21 Å. Bi(1) is bonded in an octahedral geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Bi(1)-F(1) bond lengths are 2.31 Å. Both Bi(1)-F(2) bond lengths are 2.27 Å. Both Bi(1)-F(3) bond lengths are 2.29 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Na(2), one Na(3), and one Bi(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(3), and one Bi(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Bi(1) atom.