Na16Ba6N crystallizes in the cubic Im-3m space group. There are two inequivalent Na sites. In the first Na site, Na(2) is bonded in a 10-coordinate geometry to two equivalent Na(1), six equivalent Na(2), and two equivalent Ba(1) atoms. In the second Na site, Na(1) is bonded to six equivalent Na(2) and six equivalent Ba(1) atoms to form NaBa6Na6 cuboctahedra that share corners with six equivalent Na(1)Ba6Na6 cuboctahedra, faces with six equivalent Na(1)Ba6Na6 cuboctahedra, and faces with two equivalent N(1)Ba6 octahedra. Ba(1) is bonded in a single-bond geometry to four equivalent Na(1), four equivalent Na(2), and one N(1) atom. N(1) is bonded to six equivalent Ba(1) atoms to form NBa6 octahedra that share faces with eight equivalent Na(1)Ba6Na6 cuboctahedra.
Na16Ba6N crystallizes in the cubic Im-3m space group. There are two inequivalent Na sites. In the first Na site, Na(2) is bonded in a 10-coordinate geometry to two equivalent Na(1), six equivalent Na(2), and two equivalent Ba(1) atoms. Both Na(2)-Na(1) bond lengths are 3.54 Å. There are four shorter (3.61 Å) and two longer (3.78 Å) Na(2)-Na(2) bond lengths. Both Na(2)-Ba(1) bond lengths are 4.30 Å. In the second Na site, Na(1) is bonded to six equivalent Na(2) and six equivalent Ba(1) atoms to form NaBa6Na6 cuboctahedra that share corners with six equivalent Na(1)Ba6Na6 cuboctahedra, faces with six equivalent Na(1)Ba6Na6 cuboctahedra, and faces with two equivalent N(1)Ba6 octahedra. All Na(1)-Ba(1) bond lengths are 4.39 Å. Ba(1) is bonded in a single-bond geometry to four equivalent Na(1), four equivalent Na(2), and one N(1) atom. The Ba(1)-N(1) bond length is 2.84 Å. N(1) is bonded to six equivalent Ba(1) atoms to form NBa6 octahedra that share faces with eight equivalent Na(1)Ba6Na6 cuboctahedra.