Supramolecular assembly in designing co-crystals of fumaric acid and pyrimidine/picolinate derivatives

Kansiz S., Azam M., DEGE N., Ermis N., Al-Resayes S., Alam M.

GREEN CHEMISTRY LETTERS AND REVIEWS, vol.15, no.3, pp.825-836, 2022 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 15 Issue: 3
  • Publication Date: 2022
  • Doi Number: 10.1080/17518253.2022.2130016
  • Journal Name: GREEN CHEMISTRY LETTERS AND REVIEWS
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, CAB Abstracts, Chemical Abstracts Core, Environment Index, Geobase, Directory of Open Access Journals
  • Page Numbers: pp.825-836
  • Keywords: Synthesis, Supramolecular assembly, single crystal, DFT, Hirshfeld surface analyses, PHASE-TRANSITION, HYDROGEN-BONDS, FRAMEWORK, TERNARY, SALT, WEAK
  • Ondokuz Mayıs University Affiliated: Yes

Abstract

Two co-crystals possessing fumaric acid and 2-amino-4,6-dimethoxypyrimidine (1) and fumaric acid and ethyl 2-picolinate (2) were prepared. The structure of both compounds was determined using single-crystal X-ray crystallography. The asymmetric unit of cocrystal 1 formed in a triclinic system with space group P-1 consists of one 2-amino-4,6-dimethoxypyrimidine and one half of fumarate, whereas cocrystal of 2 formed in a monoclinic system with space group P2(1)/c consists of an ethyl-2-picolinate and a half of fumarate. Co-crystal 1 exhibits intramolecular O-H center dot center dot center dot N arid N-H center dot center dot center dot O hydrogen bonds as well as intermolecular N-H center dot center dot center dot O hydrogen bonds, whereas co-crystal 2 exhibits intermolecular C-H center dot center dot center dot O and O-H center dot center dot center dot N hydrogen bonds as well as weak mar stacking interactions. Intermolecular interactions were investigated using Hirshfeld surface analyses. H center dot center dot center dot H (40.9%), O center dot center dot center dot H (32.9%), and C center dot center dot center dot H (8.2%) are the major interactions in 1 and H center dot center dot center dot H (41.6%), O center dot center dot center dot H (34.8%), and C center dot center dot center dot H (8.5%) are the most common in 2. Furthermore, density functional theory (DFT) was used to investigate the structural features of the molecules using the B3LYP-D3/6-311G(d,p) basis set. Molecular electrostatic potential (MEP) surface and global reactivity descriptors for molecules were determined to explain the reactivity of molecular behavior, structural activity, and hydrogen bonds.