A homologous series of chiral bis-ketals and mixed hemiketal-ketals with rigid bicyclo [3.3. 1]- 3, 7-dioxanonane skeleton has been prepared. The crystallization mode (conglomerate or racemic compound) was established by chiral HPLC with double UV/polarimetric detection. The study of the solid-state structure by single crystal X-ray diffraction disclosed interesting CH⋯ π intermolecular interactions. Hindering of rotation of phenyl groups at (hemi) ketalic ...