Structures, Characterization and DFT Studies of Four Novel Nickel Phenanthroline Complexes

• Published in: Crystals (Basel) 2023-04, Vol.13 (5), p.738
• Main Authors: Alramadhan, Safiah A., Hammud, Hassan H., Ali, Basem F., Ghabbour, Hazem A., Sarfaraz, Sehrish, Ayub, Khurshid
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Charge density; Coordination; Crystal structure; DFT; FTIR; Geometry; Graphite; Hydrogen bonding; Ligands; Molecular orbitals; Molecular structure; Nickel; Nitrogen; Ni–phen; OFF and EF interactions; Single crystals; Solvents; Thermal analysis
• ISSN: 2073-4352; 2073-4352
• DOI: 10.3390/cryst13050738

Four Ni–phen complexes were prepared and characterized by FTIR and thermal analysis. The X-ray structure determination shows that the geometry around NiII ions in complexes 1, [Ni(phen)2(H2O)(ONO2)](NO3); 2, [Ni(phen)2(H2O)Cl]Cl; 3, [Ni(phen)(CH3CN)(ONO2)(O2NO)] and 4, [Ni(phen)3](NO3)2.H2O.C2H5OH is considerably distorted octahedral. The coordination core geometries in 1, 2, 3 and 4 are NiN4O2, NiN4OCl, NiN3O3 and NiN6, respectively. The crystal packing and crystal supramolecularity analysis of the complexes reveal the importance of aryl∙∙∙aryl interactions, and both offset face-to-face (OFF) and edge-to-face (EF) motifs are dominant. Hydrogen bonding interactions in these structures reinforce aryl∙∙∙aryl interactions. FTIR proved the coordination of M-N and M-Cl as well as the presence of nitro groups in the complexes, while thermal analysis revealed that the loss of water, chloro and nitro groups occurred before the degradation of phenanthroline ligand in the complexes. DFT study indicates that a strong correlation exists among theoretical and experimentally determined geometric parameters with distorted octahedral geometry. The charge density in HOMO is localized on the metal halogen bond and nitrate group (NO3−), whereas the LUMO cloud density is mainly distributed on the phen ring, which indicates the electroactive nature of the ring.