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Vol. 35 No. 5 (2023): Vol 35 Issue 5, 2023

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A Failed Cocrystallization Attempt Resulted in Novel First Polymorphic Structure: Crystal Structure and Hirshfeld Surface Analysis of the Polymorph of 4-Oxo-4-(pyridin-2-ylamino)butanoic Acid

https://doi.org/10.14233/ajchem.2023.27709
G.K. Radha
https://orcid.org/0000-0003-0850-6607
https://orcid.org/0000-0003-0850-6607
Mahesha
Department of Studies in Physics, University of Mysore, Manasagangotri, Mysuru-570005, India
https://orcid.org/0000-0002-2114-3452
S. Naveen
Department of Physics, Faculty of Engineering and Technology, JAIN (Deemed-to-be University), Bengaluru-562112, India
https://orcid.org/0000-0001-6316-7973
N.K. Lokanath
Department of Studies in Physics, University of Mysore, Manasagangotri, Mysuru-570005, India
https://orcid.org/0000-0003-2773-2247
P.A. Suchetan
Department of Studies and Research in Chemistry, University College of Science, Tumkur University, Tumakuru-5761033, India
https://orcid.org/0000-0002-0322-4160

Corresponding Author(s) : P.A. Suchetan

pasuchetan@gmail.com

Asian Journal of Chemistry, Vol. 35 No. 5 (2023): Vol 35 Issue 5, 2023

Abstract

An attempt to cocrystallize 4-oxo-4-(pyridin-2-ylamino)butanoic acid (APS) with adipic acid in the ratio 1:1 was made. Solvent assisted grinding followed by solvent evaporation technique using ethanol as solvent yielded single crystals. Single crystal X-ray diffraction (SCXRD) studies of the obtained crystals showed that an attempt to obtain cocrystals has failed and instead has yielded a novel and very first polymorphic structure of APS (1). Compound 1 crystallizes with one molecule in the asymmetric unit in monoclinic P21/n system, whereas, the earlier reported polymorph, 2, crystallizes in triclinic P-1 system with two molecules in the asymmetric unit. The crystal structure of 1 features aminopyridine···carboxylic O-H···N and N-H···O=C interactions between molecules resulting in R22(8) supramolecular hetero-synthon, similar to that observed in polymorph 2. The R22(8) dimer propagates into a 2D sheet along the body diagonal plane (intersecting a and c axis) via a pair of C-H···O intermolecular interactions having R22(14) motif. Polymorph 2, on the other hand, features several C-H···O intermolecular interactions that extends the R22(8) supramolecular architecture into complex 1D columns. The Hirshfeld surface analyses including dnorm plots and two dimensional fingerprint analyses were conducted to confirm the presence of various hydrogen bonds/intermolecular interactions existing in the crystal structure of 1. H···H contacts (dispersion interactions) contributes most to the Hirshfeld surface with a contribution of 40.8%, followed by O···H/H···O (28.4%), C···H/H···C (12.4%), N···H/H···N (9.3%) and others (9.1%). Further, the molecular structure, crystal structure and Hirshfeld surfaces including dnorm and fingerprint plots of 1, 2 and a positional isomer 4-oxo-4-(pyridin-3-ylamino)butanoic acid (3) were compared to observe the similarities and differences in the three compounds.

Keywords

Cocrystals Polymorph X-ray diffraction Hirshfeld surface Hydrogen bonds
Radha, G., Mahesha, ., Naveen, S., Lokanath, N., & Suchetan, P. (2023). A Failed Cocrystallization Attempt Resulted in Novel First Polymorphic Structure: Crystal Structure and Hirshfeld Surface Analysis of the Polymorph of 4-Oxo-4-(pyridin-2-ylamino)butanoic Acid. Asian Journal of Chemistry, 35(5), 1146–1152. https://doi.org/10.14233/ajchem.2023.27709
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