Variations in the coordination environment of Co2+, Cu2+ and Zn2+ complexes prepared from a tridentate (imino)pyridine ligand and their structural comparisons

The variations in the coordination environment of Co(II), Cu(II) and Zn(II) complexes with the neutral, tridentate ligand bis[1-(cyclohexylimino)ethyl]pyridine (BCIP) are reported. Analogous syntheses were carried out utilizing either the M(BF4)2 · xH2O or MCl2 · xH2O metal salts (where M = Co(II), Cu(II) or Zn(II)) with one equivalent of BCIP. When the hydrated BF4- metal starting material was used, cationic, octahedral complexes of the type [M(BCIP)2]2+ were isolated as the tetrafluoroborate salt (4, 5). Conversely, when the hydrated chloride metal salt was used as the starting material, only neutral, pentacoordinate [M(BCIP)Cl2] complexes (1–3) formed. All complexes were characterized by X-ray diffraction studies. The three complexes that are five coordinate have distortions due mainly to the pyridine di-imine bite angle. The [Cu(BCIP)Cl2] (2) also exhibits deviations in the Cu(II)–Cl bond distances with values of 2.4242(9) and 2.2505(9) Å, which are not seen in the analogous Zn(II) and Co(II) structures. Similarly, the two six coordinate complexes (5, 6) are also altered by the ligand frame bite angle giving rise to distorted octahedral geometries in each complex. The [Cu(BCIP)2](BF4)2 (6) also exhibits Cu(II)–Nimine bond lengths that are on average 0.14 Å longer than those found in the analogous 5 coordinate complex, [Cu(BCIP)Cl2]. In addition to X-ray analysis, all complexes were also characterized by UV/Vis and IR spectroscopy with 1H NMR spectroscopy being used for the analysis of the Zn(II) analogue (3).

Graphical abstractVariations in the coordination environment of Co(II), Cu(II) and Zn(II) complexes with the neutral, tridentate ligand bis[1-(cyclohexylimino)ethyl]pyridine (BCIP) are reported. Analogous syntheses were carried out utilizing either the M(BF4)2 · xH2O or MCl2 · xH2O metal salts (where M = Co(II), Cu(II) or Zn(II)) with one equivalent of BCIP. When the hydrated BF4- metal starting material was used, cationic, octahedral complexes of the type [M(BCIP)2]2+ were isolated as the tetrafluoroborate salt. Conversely, when the hydrated chloride metal salt was used as the starting material, only neutral, pentacoordinate [M(BCIP)Cl2] complexes formed. All complexes were characterized by X-ray diffraction studies and comparisons between the complexes are made.Figure optionsDownload full-size imageDownload as PowerPoint slide