Li6Zr6HCl18 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one Cl(2), two equivalent Cl(1), and three equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with three equivalent Zr(1)HCl5 octahedra, edges with three equivalent Li(1)Cl6 octahedra, and edges with three equivalent Zr(1)HCl5 octahedra. The corner-sharing octahedral tilt angles range from 7-18°. Zr(1) is bonded to one H(1), one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form ZrHCl5 octahedra that share  a cornercorner with one Zr(1)HCl5 octahedra, corners with three equivalent Li(1)Cl6 octahedra, edges with three equivalent Li(1)Cl6 octahedra, and edges with four equivalent Zr(1)HCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. H(1) is bonded in an octahedral geometry to six equivalent Zr(1) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Zr(1) atoms. In the second Cl site, Cl(2) is bonded in a T-shaped geometry to one Li(1) and two equivalent Zr(1) atoms. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to three equivalent Li(1) and one Zr(1) atom.
Li6Zr6HCl18 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one Cl(2), two equivalent Cl(1), and three equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with three equivalent Zr(1)HCl5 octahedra, edges with three equivalent Li(1)Cl6 octahedra, and edges with three equivalent Zr(1)HCl5 octahedra. The corner-sharing octahedral tilt angles range from 7-18°. The Li(1)-Cl(2) bond length is 2.65 Å. There is one shorter (2.72 Å) and one longer (2.87 Å) Li(1)-Cl(1) bond length. There are a spread of Li(1)-Cl(3) bond distances ranging from 2.46-2.56 Å. Zr(1) is bonded to one H(1), one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form ZrHCl5 octahedra that share  a cornercorner with one Zr(1)HCl5 octahedra, corners with three equivalent Li(1)Cl6 octahedra, edges with three equivalent Li(1)Cl6 octahedra, and edges with four equivalent Zr(1)HCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. The Zr(1)-H(1) bond length is 2.26 Å. The Zr(1)-Cl(3) bond length is 2.74 Å. Both Zr(1)-Cl(1) bond lengths are 2.59 Å. There is one shorter (2.57 Å) and one longer (2.58 Å) Zr(1)-Cl(2) bond length. H(1) is bonded in an octahedral geometry to six equivalent Zr(1) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Zr(1) atoms. In the second Cl site, Cl(2) is bonded in a T-shaped geometry to one Li(1) and two equivalent Zr(1) atoms. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to three equivalent Li(1) and one Zr(1) atom.