NaW6CCl18 crystallizes in the hexagonal P6_3/m space group. Na(1) is bonded to six equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with six equivalent W(1)CCl5 octahedra. The corner-sharing octahedral tilt angles are 48°. W(1) is bonded to one C(1), one Cl(1), one Cl(2), one Cl(3), and two equivalent Cl(4) atoms to form distorted WCCl5 octahedra that share  a cornercorner with one Na(1)Cl6 octahedra, corners with two equivalent W(1)CCl5 octahedra, edges with two equivalent W(1)CCl5 octahedra, and  a faceface with one W(1)CCl5 octahedra. The corner-sharing octahedral tilt angles range from 42-48°. C(1) is bonded in a distorted pentagonal pyramidal geometry to six equivalent W(1) atoms. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a bent 120 degrees geometry to one Na(1) and one W(1) atom. In the second Cl site, Cl(2) is bonded in a distorted L-shaped geometry to two equivalent W(1) atoms. In the third Cl site, Cl(3) is bonded in a distorted L-shaped geometry to two equivalent W(1) atoms. In the fourth Cl site, Cl(4) is bonded in a 2-coordinate geometry to two equivalent W(1) atoms.
NaW6CCl18 crystallizes in the hexagonal P6_3/m space group. Na(1) is bonded to six equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with six equivalent W(1)CCl5 octahedra. The corner-sharing octahedral tilt angles are 48°. All Na(1)-Cl(1) bond lengths are 2.98 Å. W(1) is bonded to one C(1), one Cl(1), one Cl(2), one Cl(3), and two equivalent Cl(4) atoms to form distorted WCCl5 octahedra that share  a cornercorner with one Na(1)Cl6 octahedra, corners with two equivalent W(1)CCl5 octahedra, edges with two equivalent W(1)CCl5 octahedra, and  a faceface with one W(1)CCl5 octahedra. The corner-sharing octahedral tilt angles range from 42-48°. The W(1)-C(1) bond length is 2.17 Å. The W(1)-Cl(1) bond length is 2.46 Å. The W(1)-Cl(2) bond length is 2.45 Å. The W(1)-Cl(3) bond length is 2.46 Å. Both W(1)-Cl(4) bond lengths are 2.40 Å. C(1) is bonded in a distorted pentagonal pyramidal geometry to six equivalent W(1) atoms. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a bent 120 degrees geometry to one Na(1) and one W(1) atom. In the second Cl site, Cl(2) is bonded in a distorted L-shaped geometry to two equivalent W(1) atoms. In the third Cl site, Cl(3) is bonded in a distorted L-shaped geometry to two equivalent W(1) atoms. In the fourth Cl site, Cl(4) is bonded in a 2-coordinate geometry to two equivalent W(1) atoms.