A Network of Small Molecules Connected by Cross-Linked NH Bonds

• Published in: Crystal growth & design 2010-01, Vol.10 (1), p.244-251
• Main Authors: Angelici, Gaetano, Castellucci, Nicola, Contaldi, Simone, Falini, Giuseppe, Hofmann, Hans-Jörg, Monari, Magda, Tomasini, Claudia
• Format: Article
• Language: English
• Subjects: Condensed matter: structure, mechanical and thermal properties; Crystalline state (including molecular motions in solids); Crystallographic aspects of phase transformations; pressure effects; Equations of state, phase equilibria, and phase transitions; Exact sciences and technology; Physics; Solid-solid transitions; Specific phase transitions; Structure of solids and liquids; crystallography; Structure of specific crystalline solids
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg900874f

The synthesis of the small pseudopeptide Boc-l-Phe-d-Imz-OBn (Imz = imidazolidin-2-one-4-carboxylate) is reported. Crystallization of this peptide from methanol, ethanol, and isopropanol leads to isostructural solvates when the solvent is methanol or ethanol with a peptide/solvent ratio of 2:1 and to an unsolvated polymorph in the case of isopropanol. The solvate peptide crystallizes forming infinite chains with the monomers in parallel orientation connected by a single hydrogen bond. The chains are arranged in antiparallel direction and cross-linked through the NH group of the imidazolidin heterocycle with formation of a stable two-dimensional (2D) network. Crystals from isopropanol form a different 2D network. The degree of order in the crystal assembly decreases from methanol and ethanol solvates to the unsolvated pseudopeptide grown from isopropanol. Quantum chemical calculations at the HF/6-31G* level of ab initio MO theory, carried out on the two different packings, show a slight preference for the unsolvated packing.