Efficient Synthesis, SC-XRD, and Theoretical Studies of O-Benzenesulfonylated Pyrimidines: Role of Noncovalent Interaction Influence in Their Supramolecular Network

Autor(es)

Ali, Akbar ^[1] ; Khalid, Muhammad ^[2] ; Rehman, Muhammad Fayyaz Ur ^[1] ; Haq, Sadia ^[2] ; Ali, Arif ^[3] ; Tahir, Muhammad Nawaz ^[3] ; Ashfaq, Muhammad ^[3] ; Rasool, Faiz ^[2] ; Braga, Ataualpa Albert Carmo ^[4]

Afiliação do(s) autor(es)

^[1] Univ Sargodha, Dept Chem, Sargodha 40100 - Pakistan

^[2] Khwaja Fareed Univ Engn & Informat Technol, Dept Chem, Rahim Yar Khan 64200 - Pakistan

^[3] Univ Sargodha, Dept Phys, Sargodha 40100 - Pakistan

^[4] Univ Sao Paulo, Dept Quim Fundamental, Inst Quim, BR-05508000 Sao Paulo - Brazil

• Tipo de documento: Artigo Científico
• Fonte: ACS OMEGA; v. 5, n. 25, p. 15115-15128, JUN 30 2020.
• Citações Web of Science: 2

Resumo

Crystalline organic compounds, 2-amino-6-methylpyrimidin-4-yl benzenesulfonate (AMPBS) and 2,6-diaminopyrimidin-4-yl benzenesulfonate (DAPBS), were prepared via O-benzenesulfonylation of 2-amino-6-methylpyrimidin-4-ol 1 and 2,6-diaminopyrimidin-4-ol 2, respectively. The structural interpretations were achieved unambiguously by single-crystal X-ray diffraction (SC-XRD) analysis. The Hirshfeld surface study showed that C-H center dot center dot center dot O, N-H center dot center dot center dot N, and especially C-H center dot center dot center dot C hydrogen bond interactions are the key contributors to the intermolecular stabilization in the crystal. Density functional theory (DFT) studies were used to obtain a better understanding of natural bond orbitals (NBOs) and nonlinear optical (NLO) analysis for AMPBS and DAPBS at the B3LYP/6-311G(d,p) level. The time-dependent density functional theory (TD-DFT)/CAM-B3LYP/6-311G(d,p) level was employed for frontier molecular orbital analysis of both compounds. DFT-based vibrations for C-H, C-N, N-H, and stretching for C-C were found to be in good agreement with the experimental data. Overall, the theoretical findings were acquired in correspondence to the SC-XRD-based parameters. Intracharge transfer occurred in AMPBS and DAPBS compounds, which was evaluated through FMO activity. Global reactivity indices had been acquired utilizing energies of HOMO-LUMO orbitals. Overall, the theoretical findings related to AMPBS and DAPBS consist of promising correspondence to experimental findings. The theoretical-based study also exhibited that both AMPBS and DAPBS compounds contain promising NLO features. (AU)

• Processo FAPESP: 15/01491-3 - Estudo teórico das reações de acoplamento-cruzado: catálise homogênea e heterogênea
• Beneficiário: Ataualpa Albert Carmo Braga
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 14/25770-6 - Novas fronteiras em reações de acoplamento cruzado mediadas por paládio: associando catálise enantiosseletiva, ativações C-H, novos materiais e reações em fluxo visando alta eficiência e sustentabilidade em processos sintéticos
• Beneficiário: Carlos Roque Duarte Correia
• Modalidade de apoio: Auxílio à Pesquisa - Temático