LiClO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cl(1)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Cl(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Cl(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cl(1) atom. Cl(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form ClO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°.
LiClO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cl(1)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. Both Li(1)-O(1) bond lengths are 2.12 Å. Both Li(1)-O(2) bond lengths are 1.98 Å. Both Li(1)-O(3) bond lengths are 2.35 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Cl(1) atom. The O(1)-Cl(1) bond length is 1.45 Å. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Cl(1) atom. The O(2)-Cl(1) bond length is 1.43 Å. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cl(1) atom. The O(3)-Cl(1) bond length is 1.44 Å. Cl(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form ClO4 tetrahedra that share corners with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°.