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Heptakis(2,6-di-O-ethyl)-β-cyclodextrin (DE-β-CD) was crystallized in two forms from hexane and 95% aqueous methanol, respectively: A form I crystal with the space group P2 1 2 1 2 1 and a form II crystal with the space group P3 1 . In both crystals, DE-β-CD molecules are in a round shape with intramolecular O-3-H...O-2 hydrogen bonds. In the form I crystal, the DE-β-CD...