NaScCl4 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 Sc(1)Cl6 octahedra, and  an edgeedge with one Sc(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. Sc(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form ScCl6 octahedra that share corners with six equivalent Na(1)Cl6 octahedra,  an edgeedge with one Na(1)Cl6 octahedra, and edges with two equivalent Sc(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. 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 Sc(1) atom. In the second Cl site, Cl(2) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Sc(1) atoms.
NaScCl4 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 Sc(1)Cl6 octahedra, and  an edgeedge with one Sc(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. Both Na(1)-Cl(2) bond lengths are 2.87 Å. There are two shorter (2.78 Å) and two longer (2.79 Å) Na(1)-Cl(1) bond lengths. Sc(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form ScCl6 octahedra that share corners with six equivalent Na(1)Cl6 octahedra,  an edgeedge with one Na(1)Cl6 octahedra, and edges with two equivalent Sc(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. Both Sc(1)-Cl(1) bond lengths are 2.41 Å. There are two shorter (2.52 Å) and two longer (2.59 Å) Sc(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 Sc(1) atom. In the second Cl site, Cl(2) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Sc(1) atoms.