Na3CrCl6 is Ilmenite-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to six equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with twelve equivalent Na(2)Cl6 pentagonal pyramids and edges with three equivalent Cr(1)Cl6 octahedra. In the second Na site, Na(2) is bonded to six equivalent Cl(1) atoms to form distorted NaCl6 pentagonal pyramids that share corners with three equivalent Cr(1)Cl6 octahedra, corners with six equivalent Na(1)Cl6 octahedra, edges with three equivalent Na(2)Cl6 pentagonal pyramids, and  a faceface with one Cr(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. Cr(1) is bonded to six equivalent Cl(1) atoms to form CrCl6 octahedra that share corners with six equivalent Na(2)Cl6 pentagonal pyramids, edges with three equivalent Na(1)Cl6 octahedra, and faces with two equivalent Na(2)Cl6 pentagonal pyramids. Cl(1) is bonded in a distorted see-saw-like geometry to one Na(1), two equivalent Na(2), and one Cr(1) atom.
Na3CrCl6 is Ilmenite-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to six equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with twelve equivalent Na(2)Cl6 pentagonal pyramids and edges with three equivalent Cr(1)Cl6 octahedra. All Na(1)-Cl(1) bond lengths are 2.78 Å. In the second Na site, Na(2) is bonded to six equivalent Cl(1) atoms to form distorted NaCl6 pentagonal pyramids that share corners with three equivalent Cr(1)Cl6 octahedra, corners with six equivalent Na(1)Cl6 octahedra, edges with three equivalent Na(2)Cl6 pentagonal pyramids, and  a faceface with one Cr(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. There are three shorter (2.73 Å) and three longer (2.85 Å) Na(2)-Cl(1) bond lengths. Cr(1) is bonded to six equivalent Cl(1) atoms to form CrCl6 octahedra that share corners with six equivalent Na(2)Cl6 pentagonal pyramids, edges with three equivalent Na(1)Cl6 octahedra, and faces with two equivalent Na(2)Cl6 pentagonal pyramids. All Cr(1)-Cl(1) bond lengths are 2.37 Å. Cl(1) is bonded in a distorted see-saw-like geometry to one Na(1), two equivalent Na(2), and one Cr(1) atom.