Optically active derivatives of terephthalic acid: four crystal structures from two powder patterns

A novel important class of nanoporous crystalline solids, metal–organic frameworks (MOFs), composed of organic ligands (linkers) and metal ions, is now considered as a platform for the development of various functional hybrid materials. In order to design new MOF-based asymmetric catalysts, two terephthalic acid derivatives, namely 2-{[1-(1- tert -butoxycarbonyl)-L-prolyl]amino}terephthalic acid, C 18 H 22 N 2 O 7 , (1), and 2-(L-prolylamino)terephthalic acid, C 13 H 14 N 2 O 5 , (2), which could find potential applications as chiral linkers for the construction of enantioselective MOFs, were synthesized and their powder samples were measured at synchrotron station ID22 (ESRF). Each sample contained two unknown crystalline phases, so four new crystal structures were determined, namely, the 2.24-hydrate of (1), (1 a ) (space group C 222 1 ), and the 2.08-hydrate of (1), (1 b ) ( P 222 1 ), which are crystallohydrates, and two polymorphs of (2), i.e. (2 a ) ( C 222 1 ) and (2 b ) ( P 2 1 2 1 2 1 ), and were validated with DFT-d (dispersion-corrected density functional theory) optimizations.