Design and Synthesis of a <i>C</i>₂-Symmetric Self-Complementary Hydrogen-Bonding Cleft Molecule Based on the Bicyclo[3.3.1]nonane and 4-Oxo-5-azaindole Framework. Formation of Channels and Inclusion Complexes in the Solid State

The synthesis of a C2-symmetric cleft molecule 2 based on the fused framework between bicyclo[3.3.1]nonane and 4-oxo-5-azaindole, incorporating a self-complementary hydrogen-bonding motif, in both racemic and enantiomerically pure forms is reported. This cleft molecule is reminiscent of analogues of Tröger's base though with different cleft dimensions and tilt angles. The framework of 2 provides a building block for the construction of self-assembled hydrogen-bonded supramolecular structures. The solid-state structure of 2 is highly influenced by the limited solubility of (±)-2 and (−)-2. The solvents interact with the potential hydrogen-bonding motifs of (±)-2 and (−)-2, forming different three-dimensional structures as revealed by X-ray diffraction analysis. In the solid state (±)-(2)2·5DMF forms hydrogen-bonded pleated band structures that build up three-dimensional pens between adjacent bands in which two molecules of DMF are trapped. In contrast, the aggregate obtained from (−)-2, (−)-2·2AcOH, showed infinite bands of complex constitution.