Sienkiewicz-Gromiuk, J.; Drzewiecka-Antonik, A. Neutral and Ionic Form of (Benzylthio)Acetic Acid in Novel Aminopyrimidine Based Multi-Component Crystalline Phases. Crystals2023, 13, 1628.
Sienkiewicz-Gromiuk, J.; Drzewiecka-Antonik, A. Neutral and Ionic Form of (Benzylthio)Acetic Acid in Novel Aminopyrimidine Based Multi-Component Crystalline Phases. Crystals 2023, 13, 1628.
Sienkiewicz-Gromiuk, J.; Drzewiecka-Antonik, A. Neutral and Ionic Form of (Benzylthio)Acetic Acid in Novel Aminopyrimidine Based Multi-Component Crystalline Phases. Crystals2023, 13, 1628.
Sienkiewicz-Gromiuk, J.; Drzewiecka-Antonik, A. Neutral and Ionic Form of (Benzylthio)Acetic Acid in Novel Aminopyrimidine Based Multi-Component Crystalline Phases. Crystals 2023, 13, 1628.
Abstract
The (benzylthio)acetic acid (HBTA) and some aminopyrimidines, namely 2-aminopyrimidine (2-AP), 5-aminopyrimidine (5-AP), 2-amino-4,6-dimethylpyrimidine (2-A-4,6-DMP) and 2,4,6-triaminopyrimidine (2,4,6-TAP), were successfully embodied as structural units into the construction of a total of four novel supramolecular organic frameworks. The received crystalline solids were inspected by single crystal X-ray diffraction (SC XRD) in order to obtain insight into the structural and supramolecular facets. The SOFs deriving from 2-AP, 5-AP as well as 2-A-4,6-DMP crystallize in the form of true co-crystals (1-3), while the one originating from 2,4,6-TAP crystallizes as salt solvate (4). The SC XRD results indicated the different contents of structural residues present in the asymmetric units of the crystals 1-4 despite the using the same molar ratio of molecular co-formers in each case. The molecular structures of co-crystals 1-3 consist of either one neutral residue of each starting components (1 and 3) or a half nonionized residue of aminopyrimidine ingredient and one neutral residue of acidic specie (2). The asymmetric unit of salt solvate 4 is composed of two ionized residues of each co-former (two 2,4,6-TAP+ cations and two BTA- anions) and one MeOH solvent molecule. The most extensive H-bonding network is observed in the crystal structure of salt solvate 4. The relevant molecular ingredients in co-crystals 1-3 are mainly hold together by the neutral Ocarboxylic–H···Npyrimidine and Namine–H···Ocarboxylic H-bonds. In the case of aggregate 4, the corresponding ionic residues are predominantly sustained by the charged-assisted Npyrimidinium–H···Ocarboxylate and Namine–H···Ocarboxylate hydrogen interactions. The MeOH solvent incorporated into the crystal lattice of adduct 4 is also involved in H-bonding by simultaneously serving as the single donor in OMeOH–H···S and the single acceptor in Namine–H···OMeOH H-bonds afforded the structural diversity within the 2,4,6-TAP+ cations and BTA- anions. Other weaker sets of additional non-covalent contacts existing in the crystal structures of analyzed conglomerates are involved in the self-assembly, stabilization and expansion of total supramolecular organic frameworks. The fact of the formation of non-covalent bonded supramolecular organic frameworks in question is also reflected in corresponding results obtained through elemental analysis (EA), Fourier transform infrared spectroscopy (FT−IR) and thermal analysis (TG/DSC).
Keywords
(benzylthio)acetic acid; aminopyrimidines; supramolecular organic frameworks (SOFs); co-crystal; salt solvate; nonbonding contacts; SC XRD structural analysis; FT-IR spectroscopy; thermal study
Subject
Chemistry and Materials Science, Other
Copyright:
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