Never-Ending Story: New Cyclodextrin-Based Metal-Organic Framework Crystal Structures Obtained Using Different Crystallization Methods

Six novel cyclodextrin (CD)-based metal-organic frameworks (MOFs) were synthesized using distinct crystallization methodologies. A modified vapor diffusion method is introduced for the first time, termed fast crystallization, which enables the rapid solid-state formation of MOF compounds. This innovative method yielded four of the newly synthesized MOFs. The crystal structures of five obtained frameworks were structurally characterized through single-crystal X-ray diffraction, while one, compound 5 (gamma-CD-K-5), was additionally characterized as a bulk powder. Structural analysis revealed that two of the newly obtained MOFs, namely, compound 2 (alpha-CD-K-2) and compound 3 (alpha-CD-Rb-3), exhibited isostructural characteristics, forming a three-dimensional (3D) framework. Compound 1 (alpha-CD-K-1) shared the same space group as EVEGET (alpha-CD-K) and displayed the same framework type. Furthermore, the crystal packing of compound 4 (beta-CD-K-4) closely resembled that of compound 1 and EVEGET, with the only distinction lying in the type of CD employed. Notably, compound 6 (gamma-CD-K-6) incorporated an iodine ion with an occupancy of 0.2. To discern the intermolecular interactions within the obtained MOFs, the Hirshfeld surface was calculated using Crystal Explorer software.