Concomitant Polymorphs of Aryl-Ether Amine via Catemer and Dimer Carboxylic Acid Supramolecular Interactions and Their Effect on Optical Band Gap

Abstract

Carboxylic acid supramolecular synthon exhibited dimer or catemer motifs in the crystal lattice depend on the substituent and other functional groups present in the structure. In general, presence of other competing functional groups produced catemer motifs, whereas unsubstituted acids showed dimer. In this manuscript, we have synthesized a new aryl ether amine-based Schiff base with carboxylic acid functionality (1) and demonstrated polymorphic structure via catemer (1a) and dimer (1 b) motifs in the solid state. In both the structure, carboxylic acid group adopted different orientation in the crystal lattice. The different H-bonding lead to modulation of optical properties that was further supported highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) calculation. Further the stability calculation indicates that dimer (1 b) structure was more stable by 8.54 kcal/mole relative to catemer (1a) motifs. Further, the supramolecular interactions in catemer (1a) and dimer (1 b) motifs was studied by Hirshfeld surface and fingerprint plots to gain insight and compare the different functional groups contribution for intermolecular interactions in the polymorphic crystals which clearly showed different intermolecular interactions in polymorphs.

Keywords:

• Aryl ether amine
• catemer
• polymorphic structure
• supramolecular interactions

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Availability of data and material

CCDC Nos. − 1823901 (1a) and 1823902 (1 b) contain the supplementary crystallographic data for this paper.

Authors' contributions

Mehboobali Pannipara: Methodology and Writing - original draft. Abdullah G. Al-Sehemi: Conceptualization.

Additional information

Funding

This work was funded by King Khalid University through research group project under grant number R.G.P.1/35/42.