LiW6CCl18 crystallizes in the hexagonal P6_3/m space group. Li(1) is bonded to six equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with six equivalent W(1)CCl5 octahedra. The corner-sharing octahedral tilt angles are 46°. W(1) is bonded to one C(1), one Cl(2), one Cl(3), one Cl(4), and two equivalent Cl(1) atoms to form WCCl5 octahedra that share  a cornercorner with one Li(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 43-46°. 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 2-coordinate geometry to two equivalent W(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one W(1) atom. In the third Cl site, Cl(3) is bonded in a 2-coordinate 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.
LiW6CCl18 crystallizes in the hexagonal P6_3/m space group. Li(1) is bonded to six equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with six equivalent W(1)CCl5 octahedra. The corner-sharing octahedral tilt angles are 46°. All Li(1)-Cl(2) bond lengths are 2.78 Å. W(1) is bonded to one C(1), one Cl(2), one Cl(3), one Cl(4), and two equivalent Cl(1) atoms to form WCCl5 octahedra that share  a cornercorner with one Li(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 43-46°. The W(1)-C(1) bond length is 2.16 Å. The W(1)-Cl(2) bond length is 2.46 Å. The W(1)-Cl(3) bond length is 2.44 Å. The W(1)-Cl(4) bond length is 2.45 Å. There is one shorter (2.39 Å) and one longer (2.40 Å) W(1)-Cl(1) bond length. 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 2-coordinate geometry to two equivalent W(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one W(1) atom. In the third Cl site, Cl(3) is bonded in a 2-coordinate 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.