NaLuCl4 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. Na(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with six equivalent Lu(1)Cl6 octahedra, and  an edgeedge with one Lu(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Lu(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form LuCl6 octahedra that share corners with six equivalent Na(1)Cl6 octahedra,  an edgeedge with one Na(1)Cl6 octahedra, and edges with two equivalent Lu(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Lu(1) atom. In the second Cl site, Cl(2) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Lu(1) atoms.
NaLuCl4 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. Na(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with six equivalent Lu(1)Cl6 octahedra, and  an edgeedge with one Lu(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Both Na(1)-Cl(2) bond lengths are 2.88 Å. There are two shorter (2.79 Å) and two longer (2.80 Å) Na(1)-Cl(1) bond lengths. Lu(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form LuCl6 octahedra that share corners with six equivalent Na(1)Cl6 octahedra,  an edgeedge with one Na(1)Cl6 octahedra, and edges with two equivalent Lu(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Both Lu(1)-Cl(1) bond lengths are 2.49 Å. There are two shorter (2.59 Å) and two longer (2.66 Å) Lu(1)-Cl(2) bond lengths. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Lu(1) atom. In the second Cl site, Cl(2) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Lu(1) atoms.