The cyclophosphazene hydrazides N3P3(N(Me)NH2)(6) (1), spiro-N3P3(C12H8O2)(N(Me)NH2)(4) (2), and dispiro-N3P3(C12H8O2)(2)(N(Me)NH2)(2) (3) have been readily elaborated by a click synthesis involving condensation with pentafluorobenzaldehyde to afford the fluorine-rich cyclophosphazene hydrazones N3P3(N(Me)NCHC6F5)(6) (4), spiro-N3P3(C12H8O2)(N(Me)NCHC6F5)(4) (5), and dispiro-N3P3(C12H8O2)(2)(N(Me)NCHC6F5)(2) (6) in excellent yields. The molecular and crystal structures of 4-6 are reported. The crystal structures of 4-6 eveal a rich interplay of various intermolecular secondary interactions generating novel supramolecular architectures. The dependence of the molecular symmetry on the eventual supramolecular structures is also revealed. The crystal structure of 6 shows the selective entrapment of guest dioxane molecules.
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