Intriguing Case of Pseudo-Isomorphism between Chiral and Racemic Crystals of rac- and (S)/(R)2-(1,8-Naphthalimido)-2-quinuclidin-3-yl, and Their Reactivity Toward I2 an

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• 作者：Simone d’Agostino ; Dario Braga ; Fabrizia Grepioni ; Paola Taddei
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：February 5, 2014
• 年：2014
• 卷：14
• 期：2
• 页码：821-829
• 全文大小：501K
• ISSN：1528-7505

文摘

Condensation reactions between 1,8-naphthalic anhydride and racemic 3-aminoquinuclidine or chiral (S) or (R)-(鈭?-3-aminoquinuclidine allowed preparation of three novel racemic and enantiopure aza-donor ligands, namely NMiABCO (1), (S)NMiABCO (2a), and (R)NMiABCO (2b). Racemic NMiABCO (1) crystallizes in the monoclinic space group P2₁/c, Z鈥?= 1, while enantiopure (S)NMiABCO (2a) and (R)NMiABCO (2b) crystallize in the chiral monoclinic space group P2₁, Z鈥?= 2, and show significant pseudocentrosymmetry, being pseudo-isomorphous with racemic NMiABCO (1). Reactivity of both racemic and enantiopure NMiABCO toward iodine and interhalogen IBr was also investigated as a way to remove the pseudoisomorphism, yielding the three new molecular adducts [NMiABCO路I₂] (3), [(S)NMiABCO路I₂]路xCHCl₃ (4), [(S)NMiABCO路IBr]路xCHCl₃ (5) and the molecular salt [HNMiABCO][IBr₂] (6). Synthesis of complexes 3 and 4 was also carried out in the solid state via kneading and vapor digestion techniques. All compounds were fully characterized via single crystal and powder X-ray diffraction and Raman spectroscopy.