3,6-diazatetraasterane　and　3,9-diazatetraasterane　are　diazatetraasterane　derivatives　and　cage-dimers　of　1,4-dihydropyridine　in　head-to-head　or　head-to-tail　manner　by　the　regioselective　[2　+　2]　photocycloaddition.　They　were　synthesized　and　their　structures　were　verified　by　NMR　spectra,　high-resolution　mass　spectrometry,　and　Single-crystal　X-ray　diffraction.　The　results　showed　that　the　molecular　structure　of　3,6-diazatetraasterane　with　a　C　1　symmetric　property　and　the　3,9-diazatetraasterane　with　a　C　2　symmetric　property.　The　molecular　packing　arrangement　of　3,6-diazatetraasterane　was　in　the　zigzag-shape,　and　the　3,9-diazatetraasterane　was　in　layer-like　architecture.　The　non-covalent　interaction　(NCI)　and　Hirshfeld　surface　analysis　were　conducted　to　characterize　and　visualize　the　intramolecular　and　intermolecular　interactions.　The　molecular　electrostatic　potential　(MEP)　was　calculated　to　predict　electrophilic　and　nucleophilic　regions.　The　results　will　provide　a　theoretical　basis　for　further　studies　on　chemical　properties　and　pharmacological　application　of　the　azatetraasterane　derivatives.　(c)　2022　Elsevier　B.V.　All　rights　reserved.