Li2Zn(HCl2)2 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form distorted LiCl4 tetrahedra that share corners with two equivalent Li(2)H2Cl4 octahedra, corners with four equivalent Zn(1)Cl4 tetrahedra, and  an edgeedge with one Li(2)H2Cl4 octahedra. The corner-sharing octahedral tilt angles range from 85-95°. In the second Li site, Li(2) is bonded to one H(1), one H(2), one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form distorted LiH2Cl4 octahedra that share corners with two equivalent Li(1)Cl4 tetrahedra, corners with four equivalent Zn(1)Cl4 tetrahedra, and  an edgeedge with one Li(1)Cl4 tetrahedra. Zn(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form ZnCl4 tetrahedra that share corners with four equivalent Li(2)H2Cl4 octahedra and corners with four equivalent Li(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-70°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one Li(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one Li(2) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Zn(1) atom. In the second Cl site, Cl(1) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Zn(1) atom. In the third Cl site, Cl(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Zn(1) atom. In the fourth Cl site, Cl(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Zn(1) atom.
Li2Zn(HCl2)2 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form distorted LiCl4 tetrahedra that share corners with two equivalent Li(2)H2Cl4 octahedra, corners with four equivalent Zn(1)Cl4 tetrahedra, and  an edgeedge with one Li(2)H2Cl4 octahedra. The corner-sharing octahedral tilt angles range from 85-95°. The Li(1)-Cl(1) bond length is 2.57 Å. The Li(1)-Cl(2) bond length is 2.34 Å. The Li(1)-Cl(3) bond length is 2.61 Å. The Li(1)-Cl(4) bond length is 2.35 Å. In the second Li site, Li(2) is bonded to one H(1), one H(2), one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form distorted LiH2Cl4 octahedra that share corners with two equivalent Li(1)Cl4 tetrahedra, corners with four equivalent Zn(1)Cl4 tetrahedra, and  an edgeedge with one Li(1)Cl4 tetrahedra. The Li(2)-H(1) bond length is 2.28 Å. The Li(2)-H(2) bond length is 2.30 Å. The Li(2)-Cl(1) bond length is 2.77 Å. The Li(2)-Cl(2) bond length is 2.38 Å. The Li(2)-Cl(3) bond length is 2.38 Å. The Li(2)-Cl(4) bond length is 2.72 Å. Zn(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form ZnCl4 tetrahedra that share corners with four equivalent Li(2)H2Cl4 octahedra and corners with four equivalent Li(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-70°. The Zn(1)-Cl(1) bond length is 2.28 Å. The Zn(1)-Cl(2) bond length is 2.30 Å. The Zn(1)-Cl(3) bond length is 2.32 Å. The Zn(1)-Cl(4) bond length is 2.32 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one Li(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one Li(2) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Zn(1) atom. In the second Cl site, Cl(1) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Zn(1) atom. In the third Cl site, Cl(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Zn(1) atom. In the fourth Cl site, Cl(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Zn(1) atom.