Li2Zr6MnCl15 crystallizes in the tetragonal I4/mmm space group. Li(1) is bonded to two equivalent Cl(2) and four equivalent Cl(4) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with four equivalent Zr(1)MnCl5 octahedra, and edges with four equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Mn(1), one Cl(1), and four equivalent Cl(4) atoms to form ZrMnCl5 octahedra that share corners with two equivalent Zr(1)MnCl5 octahedra, corners with four equivalent Li(1)Cl6 octahedra, and edges with four equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Zr site, Zr(2) is bonded to one Mn(1), one Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms to form ZrMnCl5 octahedra that share corners with two equivalent Zr(2)MnCl5 octahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Zr(1)MnCl5 octahedra, and edges with two equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedra are not tilted. Mn(1) is bonded in an octahedral geometry to two equivalent Zr(1) and four equivalent Zr(2) atoms. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a linear geometry to two equivalent Zr(1) atoms. In the second Cl site, Cl(2) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Zr(2) atoms. In the third Cl site, Cl(3) is bonded in an L-shaped geometry to two equivalent Zr(2) atoms. In the fourth Cl site, Cl(4) is bonded in a T-shaped geometry to one Li(1), one Zr(1), and one Zr(2) atom.
Li2Zr6MnCl15 crystallizes in the tetragonal I4/mmm space group. Li(1) is bonded to two equivalent Cl(2) and four equivalent Cl(4) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with four equivalent Zr(1)MnCl5 octahedra, and edges with four equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Li(1)-Cl(2) bond lengths are 2.61 Å. All Li(1)-Cl(4) bond lengths are 2.70 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Mn(1), one Cl(1), and four equivalent Cl(4) atoms to form ZrMnCl5 octahedra that share corners with two equivalent Zr(1)MnCl5 octahedra, corners with four equivalent Li(1)Cl6 octahedra, and edges with four equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Zr(1)-Mn(1) bond length is 2.46 Å. The Zr(1)-Cl(1) bond length is 2.76 Å. All Zr(1)-Cl(4) bond lengths are 2.62 Å. In the second Zr site, Zr(2) is bonded to one Mn(1), one Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms to form ZrMnCl5 octahedra that share corners with two equivalent Zr(2)MnCl5 octahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Zr(1)MnCl5 octahedra, and edges with two equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedra are not tilted. The Zr(2)-Mn(1) bond length is 2.42 Å. The Zr(2)-Cl(2) bond length is 2.90 Å. Both Zr(2)-Cl(3) bond lengths are 2.57 Å. Both Zr(2)-Cl(4) bond lengths are 2.57 Å. Mn(1) is bonded in an octahedral geometry to two equivalent Zr(1) and four equivalent Zr(2) atoms. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a linear geometry to two equivalent Zr(1) atoms. In the second Cl site, Cl(2) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Zr(2) atoms. In the third Cl site, Cl(3) is bonded in an L-shaped geometry to two equivalent Zr(2) atoms. In the fourth Cl site, Cl(4) is bonded in a T-shaped geometry to one Li(1), one Zr(1), and one Zr(2) atom.