Na2UCl6 is beta Vanadium nitride-derived structured and crystallizes in the trigonal P-3m1 space group. Na(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent U(1)Cl6 octahedra,  an edgeedge with one U(2)Cl6 octahedra, and edges with three equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. There are two inequivalent U sites. In the first U site, U(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form UCl6 octahedra that share corners with twelve equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. In the second U site, U(2) is bonded to six equivalent Cl(3) atoms to form UCl6 octahedra that share edges with six equivalent Na(1)Cl6 octahedra. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one U(1) atom. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one U(1) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one U(2) atom.
Na2UCl6 is beta Vanadium nitride-derived structured and crystallizes in the trigonal P-3m1 space group. Na(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent U(1)Cl6 octahedra,  an edgeedge with one U(2)Cl6 octahedra, and edges with three equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. Both Na(1)-Cl(1) bond lengths are 2.83 Å. Both Na(1)-Cl(2) bond lengths are 2.94 Å. Both Na(1)-Cl(3) bond lengths are 2.84 Å. There are two inequivalent U sites. In the first U site, U(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form UCl6 octahedra that share corners with twelve equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. All U(1)-Cl(1) bond lengths are 2.65 Å. All U(1)-Cl(2) bond lengths are 2.64 Å. In the second U site, U(2) is bonded to six equivalent Cl(3) atoms to form UCl6 octahedra that share edges with six equivalent Na(1)Cl6 octahedra. All U(2)-Cl(3) bond lengths are 2.63 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one U(1) atom. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one U(1) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one U(2) atom.