Dicarboxylic Acid-Based Co-Crystals of Pyridine Derivatives Involving Structure Guiding Unconventional Synthons: Experimental and Theoretical Studies

Four co-crystals involving dicarboxylic acids and pyridine derivatives, viz. (ox)0.5(2-CNpy) (1), (adp)(4-CNpy)2 (2), (tp)(4-CNpy)2 (3) and (adp)(3-CNpy)2 (4) (ox = oxalic acid, tp = terephthalic acid, adp = adipic acid, CNpy = cyanopyridine), have been synthesized at room temperature in water mediu...

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Bibliographic Details
Published in:Crystals (Basel) 2022-10, Vol.12 (10), p.1442
Main Authors: Sharma, Pranay, Gomila, Rosa M., Frontera, Antonio, Barcelo-Oliver, Miquel, Bhattacharyya, Manjit K.
Format: Article
Language:English
Subjects:
Acids
Carboxylic acids
Chemical bonds
Chemical properties
Chemical synthesis
co-crystals
Crystal structure
Crystallization
Crystals
Density functional theory
DFT calculations
Dicarboxylic acids
Diffraction
H-bonding
Hydrogen
Ligands
Methods
nitrile–nitrile
Oxalic acid
O···π-hole
Pharmaceuticals
Porous materials
Pyridine
Pyridines
Quantum theory
Room temperature
Software
Structural analysis
Terephthalic acid
Topology
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Summary:Four co-crystals involving dicarboxylic acids and pyridine derivatives, viz. (ox)0.5(2-CNpy) (1), (adp)(4-CNpy)2 (2), (tp)(4-CNpy)2 (3) and (adp)(3-CNpy)2 (4) (ox = oxalic acid, tp = terephthalic acid, adp = adipic acid, CNpy = cyanopyridine), have been synthesized at room temperature in water medium. Crystal-structure analysis of co-crystal 1 reveals the presence of unconventional O···π(oxalic acid)-hole interaction with the C-C bond of ox moiety, along with parallel nitrile–nitrile interactions. The structural topologies of co-crystals 2–4 unfold the presence of antiparallel nitrile–nitrile interactions involving the CNpy moieties. The molecular associations involving the H-bonds and other unconventional contacts among the co-formers of the multicomponent co-crystals are analyzed using density functional theory (DFT) calculations combined with molecular electrostatic potential (MEP) surface, quantum theory of atoms-in-molecules (QTAIM) and noncovalent interaction (NCI) plot computational tools. The computational studies revealed the presence of unconventional O···π-hole interaction in 1 and the H-bonded synthons with π-stacked nitrile contacts involving CNpy moieties in co-crystals 2–4. The energetic features of the noncovalent contacts reveal the crucial roles of the H-bonding synthons and π-stacking interactions in the multicomponent compounds.
ISSN:2073-4352
2073-4352
DOI:10.3390/cryst12101442