AgClO4 crystallizes in the orthorhombic Pnma space group. Ag(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form distorted AgO6 octahedra that share corners with six equivalent Cl(1)O4 tetrahedra and edges with two equivalent Ag(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Ag(1) and one Cl(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ag(1) and one Cl(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ag(1) and one Cl(1) atom. Cl(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form ClO4 tetrahedra that share corners with six equivalent Ag(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-68°.
AgClO4 crystallizes in the orthorhombic Pnma space group. Ag(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form distorted AgO6 octahedra that share corners with six equivalent Cl(1)O4 tetrahedra and edges with two equivalent Ag(1)O6 octahedra. The Ag(1)-O(2) bond length is 2.62 Å. The Ag(1)-O(3) bond length is 2.55 Å. There are two shorter (2.55 Å) and two longer (2.71 Å) Ag(1)-O(1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Ag(1) and one Cl(1) atom. The O(1)-Cl(1) bond length is 1.48 Å. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ag(1) and one Cl(1) atom. The O(2)-Cl(1) bond length is 1.46 Å. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ag(1) and one Cl(1) atom. The O(3)-Cl(1) bond length is 1.45 Å. Cl(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form ClO4 tetrahedra that share corners with six equivalent Ag(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-68°.