The First Noncovalent-Bonded Supramolecular Frameworks of (Benzylthio)Acetic Acid with Proline Compounds, Isonicotinamide and Tryptamine

Abstract

The co-crystallization of (benzylthio)acetic acid (HBTA) with L-proline (L-PRO), D-proline (D-PRO), DL-proline (DL-PRO), isonicotinamide (INA) and tryptamine (TPA) led to the formation of five novel crystalline compounds: L-PRO^±·HBTA (1), D-PRO^±·HBTA (2), DL-PRO^±·HBTA (3), INA·HBTA (4) and TPA⁺·BTA^- (5). The prepared supramolecular assemblies were characterized by single crystal X-ray diffraction, an elemental analysis, FT-IR spectroscopy and a thermal analysis based on thermogravimetry (TG) combined with differential scanning calorimetry (DSC). Additionally, their melting points through TG/DSC measurements were established. All fabricated adducts demonstrated the same stoichiometry, displayed as 1:1. The integration of HBTA with selected N-containing co-formers yielded different forms of multi-component crystalline phases: zwitterionic co-crystals (1-3), true co-crystal (4) or true salt (5). In the asymmetric units of 1-4, the acidic ingredient is protonated, whereas the corresponding N-containing entities take either the zwitterionic form (1-3) or remain in the original neutral figure (4). The molecular structure of complex 5 is occupied by the real ionic forms of both components, namely the (benzylthio)acetate anion (BTA^-) and the tryptaminium cation (TPA⁺). In crystals 1-5, the respective molecular residues are permanently bound to each other via strong H-bonds provided by the following pairs of donor···acceptor: O_carboxylic···O_carboxylate and N_{pyrrolidinium}···O_carboxylate in 1-3, O_carboxylic···N_pyridine and N_amine···O_carboxylic in 4 as well as N_indole···O_carboxylate and N_aminium···O_carboxylate in 5. The crystal structures of conglomerates 1-5 are also stabilized by numerous weaker intermolecular contacts, including C-H···O (1-3, 5), C-H···S (1, 2, 5), C-H···N (5), C-H···C (5), C-H···π (1-5) as well as π···π (4) interactions. The different courses of registered FT-IR spectral traces and thermal profiles for materials 1-5 in relation to their counterparts, gained for the pure molecular ingredients, also clearly confirm the formation of new crystalline phases.

Keywords: (benzylthio)acetic acid; crystal structure; infrared spectra; isonicotinamide; noncovalent interactions; proline; supramolecular assemblies; thermal behaviour; tryptamine.