Topological definition of crystal structure: determination of the bonded interactions in solid molecular chlorine

The heavier halide molecules form layered crystals indicative of the presence of a specific directed intermolecular interaction. It is shown that this interaction within the crystal can be defined and characterized using the topology of the electron density within the theory of atoms in crystals. It is also shown that its presence in the crystal and the resulting geometry of the layered structure can be predicted in terms of the topology of the Laplacian distribution of an isolated Cl2 molecule, as it relates to the definition of Lewis acid and base sites within the valence shell of an atom. The generality of the definition of both primary and secondary interactions in terms of the topology of the electron density is demonstrated for all types of crystal. The electron density of solid molecular chlorine was determined by fitting the experimental X-ray structure factors and by theoretical calculation and its topology determined. Each Cl atom is found to be linked by bond paths, lines of maximum electron density, to twelve other atoms in the crystal: to four atoms in the same layer parallel to the bc plane, one of which defines the intramolecular bond of the Cl2 group, to six atoms in the four neighbouring molecules lying in the same stack parallel to the b axis and to two atoms in molecules situated in a neighbouring stack.