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Molecular crystals exhibiting polar symmetry are important paradigms for developing new electrooptical materials. Though accessing bulk polarity still presents a significant challenge, in some cases it may be rationalized as being associated with the specific molecular shapes and symmetries and subtle features of supramolecular interactions. In the crystal structure of 3,5,7-trinitro-1-azaadamantane, C9H12N4O6, the polar symmetry of the molecular arrangement is a result of complementary prerequisites, namely the C3v symmetry of the mol