Similarities and differences in the crystal packing of halogen-substituted indole derivatives.

The role of different intermolecular interactions in the crystal structures of halogen-substituted indoles which are fused with six-membered or seven-membered cyclic rings is investigated here. Several crystal structures show isostructural characteristics due to the presence of similar supramolecular motifs. In the absence of any strong hydrogen bonds, the molecular packing of reported structures is primarily stabilized by the presence of non-classical N-H...π and C-H...π interactions in addition to C-H...X (X = F/Cl/Br) interactions. The nature and energetics of primary and secondary dimeric motifs are partitioned into the electrostatics, polarization, dispersion and exchange-repulsion components using the PIXEL method. Short and directional N-H...π interactions are further explored by a topological analysis of the electron density based on quantum theory of atoms in molecules.