Synthesis of Diaminopyrimidine Sulfonate Derivatives and Exploration of Their Structural and Quantum Chemical Insights via SC-XRD and the DFT Approach

Akbar Ali; Muhammad Khalid; Muhammad Nawaz Tahir; Muhammad Imran; Muhammad Ashfaq; Riaz Hussain; Mohammed A Assiri; Imran Khan

doi:10.1021/acsomega.0c06323

Synthesis of Diaminopyrimidine Sulfonate Derivatives and Exploration of Their Structural and Quantum Chemical Insights via SC-XRD and the DFT Approach

ACS Omega. 2021 Mar 3;6(10):7047-7057. doi: 10.1021/acsomega.0c06323. eCollection 2021 Mar 16.

Authors

Akbar Ali¹, Muhammad Khalid², Muhammad Nawaz Tahir³, Muhammad Imran⁴, Muhammad Ashfaq³, Riaz Hussain⁵, Mohammed A Assiri^{4

6}, Imran Khan³

Affiliations

¹ Institute of Chemistry, University of Sargodha, Sargodha 40100, Pakistan.
² Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan.
³ Department of Physics, University of Sargodha, Sargodha 40100, Pakistan.
⁴ Department of Chemistry, Faculty of Science, King Khalid University, P.O. Box 9004, Abha 61413, Saudi Arabia.
⁵ Division of Science and Technology University of Education Lahore, Lahore 54770, Pakistan.
⁶ Research Center for Advanced Materials Science (RCAMS), King Khalid University, P.O. Box 9004, Abha 61413, Saudi Arabia.

Abstract

Two heterocyclic compounds named 2,6-diaminopyrimidin-4-ylnaphthalene-2-sulfonate (A) and 2,6-diaminopyrimidin-4-yl4-methylbenzene sulfonate (B) were synthesized. The structures of heterocyclic molecules were established by the X-ray crystallographic technique, which showed several noncovalent interactions as N···H···N, N···H···O, and C-H···O bonding and parallel offset stacking interaction. Hydrogen-bonding interactions were further explored by the Hirshfeld surface (HS) analysis. Nonlinear optical (NLO) and natural bond orbital (NBO) properties were calculated utilizing the B3LYP/6-311G(d,p) level. Frontier molecular orbitals (FMOs) and molecular electrostatic potential (MEP) were calculated utilizing the time-dependent density functional theory (TD-DFT) at the same level. The NBO analysis showed that the molecular stabilities of compounds A and B were attributed to their large stabilization energy values. The second hyperpolarizability (γ_tot) values for A and B were obtained as 3.7 × 10⁴ and 2.7 × 10⁴ au, respectively. The experimental X-ray crystallographic and theoretical structural parameters of A and B were found to be in close correspondence. Both the molecules reveal substantial NLO responses that can be significant for their utilization in advanced applications.