Synthesis of two Hofmann type and Hofmann-type-like compounds in crystal form from 4-aminopyridine and their characterizations by various methods

• Published in: Journal of molecular structure Vol. 1252; p. 132088
• Main Authors: Kartal, Zeki, Şahin, Onur
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.03.2022
• Subjects: 4-aminopyridine (4AP); DFT studies; Hofmann type complexes; Hofmann-type-like complexes; SC-XRD analysis; Vibration spectra; Hofmann type complexes; Hofmann-type-like complexes; 4-aminopyridine (4AP); DFT studies; Vibration spectra; SC-XRD analysis
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2021.132088

•Two 4-aminopyridine complexes, one of the Hofmann type and the other Hofmann-type-like, were obtained in crystal form.•Vibration and SC-XRD spectra of these complexes were recorded and their structural parameters were determined.•The elemental analyzes of these complexes were made.•DFT calculations were made on these complexes in order to obtain some new properties. This study encompasses the synthesis of two heterometallic tetracyanonickelate(II) complexes based on 4-aminopyridine (4AP) in crystalline form along an investigation of their structural properties. These complexes were characterized by using vibration spectroscopy, elemental analysis, and single crystal X-ray diffraction (SC-XRD) techniques. According to the data obtained using the SC-XRD technique, the heterometallic [Cd(4AP)2Ni(μ4CN)4]n complex has the Triclinic crystal system and the P-1 space group. The other, heterometallic [Ni(4AP)2(H2O)2Ni(μ2CN)2(CN)2]n complex, has Monoclinic crystal system and C2/c space group. The asymmetric unit of heterometallic complex 1 consists of a Ni(II) ion, a Cd(II) ion, two cyanide ligands and a 4AP ligand. Also, the asymmetric unit of complex 2 consists of two Ni(II) ions, a 4AP ligand, two cyanide ligands, and two half coordinated water molecules. The molecular modeling of these complexes was analyzed with the Gaussian 03 program. The chemical properties of the metal complexes were calculated from the resulting HOMO and LUMO values and natural bond orbital (NBO) analysis. The Investigation of the elemental, spectral and SC-XRD data of these complexes reveals that the formulas [Cd(4AP)2Ni(μ4CN)4]n (1) and [Ni(4AP)2(H2O)2Ni(μ2CN)2(CN)2]n (2) fully explain their crystal structure. [Display omitted]