Na21Ba14CaN6 crystallizes in the monoclinic C2/m space group. There are nine inequivalent Na sites. In the first Na site, Na(5) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Na(6), two equivalent Na(7), and two equivalent Ba(5) atoms. In the second Na site, Na(6) is bonded in a 9-coordinate geometry to one Na(1), one Na(3), one Na(4), one Na(5), one Na(6), one Na(7), one Ba(1), one Ba(2), and one Ba(3) atom. In the third Na site, Na(7) is bonded in a 9-coordinate geometry to one Na(3), two equivalent Na(5), two equivalent Na(6), one Ba(3), one Ba(5), and two equivalent Ba(1) atoms. In the fourth Na site, Na(8) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Ba(1), two equivalent Ba(2), two equivalent Ba(4), and two equivalent Ba(5) atoms to form distorted NaBa8Na4 cuboctahedra that share corners with four equivalent N(2)Ba5Ca octahedra, faces with two equivalent Na(8)Ba8Na4 cuboctahedra, faces with two equivalent Na(9)Ba8Na4 cuboctahedra, faces with two equivalent N(1)Ba5Ca octahedra, and faces with two equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedral tilt angles range from 15-16°. In the fifth Na site, Na(9) is bonded to two equivalent Na(2), two equivalent Na(3), four equivalent Ba(1), and four equivalent Ba(2) atoms to form distorted NaBa8Na4 cuboctahedra that share corners with four equivalent N(1)Ba5Ca octahedra, faces with four equivalent Na(8)Ba8Na4 cuboctahedra, and faces with four equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedral tilt angles are 15°. In the sixth Na site, Na(1) is bonded in a 12-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(5), one Na(6), one Na(8), two equivalent Na(4), one Ba(1), one Ba(2), one Ba(4), and one Ba(5) atom. In the seventh Na site, Na(2) is bonded in a 11-coordinate geometry to one Na(9), two equivalent Na(1), two equivalent Na(8), one Ba(4), one Ba(5), two equivalent Ba(1), and two equivalent Ba(2) atoms. In the eighth Na site, Na(3) is bonded in a 10-coordinate geometry to one Na(7), one Na(9), two equivalent Na(1), two equivalent Na(6), two equivalent Ba(1), and two equivalent Ba(2) atoms. In the ninth Na site, Na(4) is bonded in a 8-coordinate geometry to one Na(4), two equivalent Na(6), four equivalent Na(1), and one Ba(3) atom. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a single-bond geometry to one Na(1), one Na(2), one Na(3), one Na(6), one Na(7), one Na(8), one Na(9), and one N(2) atom. In the second Ba site, Ba(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(6), one Na(8), one Na(9), one N(1), and two equivalent N(2) atoms. In the third Ba site, Ba(3) is bonded in a 3-coordinate geometry to one Na(4), one Na(7), two equivalent Na(6), one N(1), and two equivalent N(2) atoms. In the fourth Ba site, Ba(4) is bonded in a 3-coordinate geometry to one Na(2), two equivalent Na(1), two equivalent Na(8), one N(1), and two equivalent N(2) atoms. In the fifth Ba site, Ba(5) is bonded in a single-bond geometry to one Na(2), one Na(7), two equivalent Na(1), two equivalent Na(5), two equivalent Na(8), and one N(1) atom. Ca(1) is bonded in an octahedral geometry to two equivalent N(1) and four equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ba(3), one Ba(4), one Ba(5), two equivalent Ba(2), and one Ca(1) atom to form distorted NBa5Ca octahedra that share corners with two equivalent Na(9)Ba8Na4 cuboctahedra,  a cornercorner with one N(1)Ba5Ca octahedra, faces with two equivalent Na(8)Ba8Na4 cuboctahedra, and faces with four equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedra are not tilted. In the second N site, N(2) is bonded to one Ba(1), one Ba(3), one Ba(4), two equivalent Ba(2), and one Ca(1) atom to form distorted NBa5Ca octahedra that share corners with two equivalent Na(8)Ba8Na4 cuboctahedra,  a cornercorner with one N(2)Ba5Ca octahedra,  a faceface with one Na(8)Ba8Na4 cuboctahedra,  a faceface with one Na(9)Ba8Na4 cuboctahedra, faces with two equivalent N(1)Ba5Ca octahedra, and faces with two equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedra are not tilted.
Na21Ba14CaN6 crystallizes in the monoclinic C2/m space group. There are nine inequivalent Na sites. In the first Na site, Na(5) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Na(6), two equivalent Na(7), and two equivalent Ba(5) atoms. Both Na(5)-Na(1) bond lengths are 3.61 Å. Both Na(5)-Na(6) bond lengths are 3.97 Å. Both Na(5)-Na(7) bond lengths are 3.89 Å. Both Na(5)-Ba(5) bond lengths are 4.27 Å. In the second Na site, Na(6) is bonded in a 9-coordinate geometry to one Na(1), one Na(3), one Na(4), one Na(5), one Na(6), one Na(7), one Ba(1), one Ba(2), and one Ba(3) atom. The Na(6)-Na(1) bond length is 3.65 Å. The Na(6)-Na(3) bond length is 3.55 Å. The Na(6)-Na(4) bond length is 3.81 Å. The Na(6)-Na(6) bond length is 3.56 Å. The Na(6)-Na(7) bond length is 3.62 Å. The Na(6)-Ba(1) bond length is 4.25 Å. The Na(6)-Ba(2) bond length is 4.46 Å. The Na(6)-Ba(3) bond length is 4.44 Å. In the third Na site, Na(7) is bonded in a 9-coordinate geometry to one Na(3), two equivalent Na(5), two equivalent Na(6), one Ba(3), one Ba(5), and two equivalent Ba(1) atoms. The Na(7)-Na(3) bond length is 3.92 Å. The Na(7)-Ba(3) bond length is 4.11 Å. The Na(7)-Ba(5) bond length is 4.17 Å. Both Na(7)-Ba(1) bond lengths are 4.04 Å. In the fourth Na site, Na(8) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Ba(1), two equivalent Ba(2), two equivalent Ba(4), and two equivalent Ba(5) atoms to form distorted NaBa8Na4 cuboctahedra that share corners with four equivalent N(2)Ba5Ca octahedra, faces with two equivalent Na(8)Ba8Na4 cuboctahedra, faces with two equivalent Na(9)Ba8Na4 cuboctahedra, faces with two equivalent N(1)Ba5Ca octahedra, and faces with two equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedral tilt angles range from 15-16°. Both Na(8)-Na(1) bond lengths are 3.81 Å. Both Na(8)-Na(2) bond lengths are 3.64 Å. Both Na(8)-Ba(1) bond lengths are 4.30 Å. Both Na(8)-Ba(2) bond lengths are 4.03 Å. Both Na(8)-Ba(4) bond lengths are 4.03 Å. Both Na(8)-Ba(5) bond lengths are 4.44 Å. In the fifth Na site, Na(9) is bonded to two equivalent Na(2), two equivalent Na(3), four equivalent Ba(1), and four equivalent Ba(2) atoms to form distorted NaBa8Na4 cuboctahedra that share corners with four equivalent N(1)Ba5Ca octahedra, faces with four equivalent Na(8)Ba8Na4 cuboctahedra, and faces with four equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedral tilt angles are 15°. Both Na(9)-Na(2) bond lengths are 3.55 Å. Both Na(9)-Na(3) bond lengths are 3.81 Å. All Na(9)-Ba(1) bond lengths are 4.47 Å. All Na(9)-Ba(2) bond lengths are 4.09 Å. In the sixth Na site, Na(1) is bonded in a 12-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(5), one Na(6), one Na(8), two equivalent Na(4), one Ba(1), one Ba(2), one Ba(4), and one Ba(5) atom. The Na(1)-Na(1) bond length is 3.75 Å. The Na(1)-Na(2) bond length is 3.90 Å. The Na(1)-Na(3) bond length is 3.94 Å. There is one shorter (3.82 Å) and one longer (3.95 Å) Na(1)-Na(4) bond length. The Na(1)-Ba(1) bond length is 4.33 Å. The Na(1)-Ba(2) bond length is 4.26 Å. The Na(1)-Ba(4) bond length is 4.26 Å. The Na(1)-Ba(5) bond length is 4.49 Å. In the seventh Na site, Na(2) is bonded in a 11-coordinate geometry to one Na(9), two equivalent Na(1), two equivalent Na(8), one Ba(4), one Ba(5), two equivalent Ba(1), and two equivalent Ba(2) atoms. The Na(2)-Ba(4) bond length is 4.15 Å. The Na(2)-Ba(5) bond length is 4.35 Å. Both Na(2)-Ba(1) bond lengths are 4.34 Å. Both Na(2)-Ba(2) bond lengths are 4.23 Å. In the eighth Na site, Na(3) is bonded in a 10-coordinate geometry to one Na(7), one Na(9), two equivalent Na(1), two equivalent Na(6), two equivalent Ba(1), and two equivalent Ba(2) atoms. Both Na(3)-Ba(1) bond lengths are 4.35 Å. Both Na(3)-Ba(2) bond lengths are 4.38 Å. In the ninth Na site, Na(4) is bonded in a 8-coordinate geometry to one Na(4), two equivalent Na(6), four equivalent Na(1), and one Ba(3) atom. The Na(4)-Na(4) bond length is 3.57 Å. The Na(4)-Ba(3) bond length is 4.17 Å. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a single-bond geometry to one Na(1), one Na(2), one Na(3), one Na(6), one Na(7), one Na(8), one Na(9), and one N(2) atom. The Ba(1)-N(2) bond length is 2.52 Å. In the second Ba site, Ba(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(6), one Na(8), one Na(9), one N(1), and two equivalent N(2) atoms. The Ba(2)-N(1) bond length is 2.76 Å. There is one shorter (2.75 Å) and one longer (2.83 Å) Ba(2)-N(2) bond length. In the third Ba site, Ba(3) is bonded in a 3-coordinate geometry to one Na(4), one Na(7), two equivalent Na(6), one N(1), and two equivalent N(2) atoms. The Ba(3)-N(1) bond length is 2.79 Å. Both Ba(3)-N(2) bond lengths are 2.81 Å. In the fourth Ba site, Ba(4) is bonded in a 3-coordinate geometry to one Na(2), two equivalent Na(1), two equivalent Na(8), one N(1), and two equivalent N(2) atoms. The Ba(4)-N(1) bond length is 2.83 Å. Both Ba(4)-N(2) bond lengths are 2.75 Å. In the fifth Ba site, Ba(5) is bonded in a single-bond geometry to one Na(2), one Na(7), two equivalent Na(1), two equivalent Na(5), two equivalent Na(8), and one N(1) atom. The Ba(5)-N(1) bond length is 2.53 Å. Ca(1) is bonded in an octahedral geometry to two equivalent N(1) and four equivalent N(2) atoms. Both Ca(1)-N(1) bond lengths are 2.58 Å. All Ca(1)-N(2) bond lengths are 2.57 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ba(3), one Ba(4), one Ba(5), two equivalent Ba(2), and one Ca(1) atom to form distorted NBa5Ca octahedra that share corners with two equivalent Na(9)Ba8Na4 cuboctahedra,  a cornercorner with one N(1)Ba5Ca octahedra, faces with two equivalent Na(8)Ba8Na4 cuboctahedra, and faces with four equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedra are not tilted. In the second N site, N(2) is bonded to one Ba(1), one Ba(3), one Ba(4), two equivalent Ba(2), and one Ca(1) atom to form distorted NBa5Ca octahedra that share corners with two equivalent Na(8)Ba8Na4 cuboctahedra,  a cornercorner with one N(2)Ba5Ca octahedra,  a faceface with one Na(8)Ba8Na4 cuboctahedra,  a faceface with one Na(9)Ba8Na4 cuboctahedra, faces with two equivalent N(1)Ba5Ca octahedra, and faces with two equivalent N(2)Ba5Ca octahedra. The corner-sharing octahedra are not tilted.