Crystalline Derivatives of Dipyrazolo-1,5-diazocine and Dipyrazolopyrimidine: A Case of Unexpected Synthesis and Isostructural Polymorphism

Pyrazole-phenylmethanimines (Shiff bases), Py-N=CH-Ph, form molecular crystals whose supramolecular and self-assembly properties can be tuned according to the substitution made on the aromatic and pyrazole rings. In pursuit of the first pyrazole-pyridinemethanimine member, Py-N=CH-Pyr, by following the well-known synthetic scheme for these Shiff bases, two hitherto unknown crystalline derivatives of dipyrazolo-1,5-diazocine and dipyrazolopyrimidine were obtained instead, this depending on the use or not of acetic acid as the catalyst. 1,5-diazocine crystallizes in a single P-1 triclinic packing system (Z = 2, Z ' = 1), while dipyrazolopyrimidine exhibits isostructural dimorphic behavior by adopting two (pale pink and yellow) alike P2(1)/c monoclinic systems (both Z = 4, Z ' = 1) as a function of the solvent used. Crystal structures were resolved by means of X-ray diffraction technique and their intramolecular, intermolecular, and supramolecular assemblies analyzed with the assistance of decorated Hirshfeld surfaces and the topology study of electron density using the quantum-theory of atoms in molecules (QTAIM). Although both dipyrazolopyrimidine polymorphs are stabilized by the same type of noncovalent motifs, the pale pink crystal has a slightly more compact structure, with more efficient inter- and intramolecular interactions.