Na3ScF6 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 Sc(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-45°. Sc(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form ScF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-45°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), two equivalent Na(1), and one Sc(1) atom to form a mixture of distorted corner and edge-sharing FNa3Sc trigonal pyramids. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(1), and one Sc(1) atom. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Sc(1) atom to form a mixture of distorted corner and edge-sharing FNa3Sc trigonal pyramids.
Na3ScF6 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 (2.28 Å) and one longer (2.53 Å) Na(1)-F(1) bond length. There is one shorter (2.28 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 2.28-2.73 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 Sc(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-45°. Both Na(2)-F(1) bond lengths are 2.27 Å. Both Na(2)-F(2) bond lengths are 2.20 Å. Both Na(2)-F(3) bond lengths are 2.30 Å. Sc(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form ScF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 37-45°. Both Sc(1)-F(1) bond lengths are 2.03 Å. Both Sc(1)-F(2) bond lengths are 2.01 Å. Both Sc(1)-F(3) bond lengths are 2.03 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), two equivalent Na(1), and one Sc(1) atom to form a mixture of distorted corner and edge-sharing FNa3Sc trigonal pyramids. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(1), and one Sc(1) atom. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(1), and one Sc(1) atom to form a mixture of distorted corner and edge-sharing FNa3Sc trigonal pyramids.