First and second coordination spheres in 8-azaxanthinato salts of divalent metal aquacomplexes – Ab initio and DFT study

The hydrogen bonding pattern in complexes of the type [M2+(H2O)6](dmax)2 (M = Mn, Ni, Co, Zn, Cd, Hdmax = 1,3-dimethyl-8-azaxanthine), [M2+(H2O)4(py)2](dmax)2 (M = Mn, Co, Zn, Cd, py = pyridine) and [M2+(dmax)2(H2O)2(py)2]·2H2O (M = Ni, Cu) were studied by ab initio (MP2/LANL2DZ//B3LYP/LANL2DZ) and density functional theory methods (B3LYP/LANL2DZ, B3LYP/6-31G∗∗ and B3PW91/6-31G∗∗). The investigation includes a variety of theoretical analyses, which include interaction energy, many body analyses, electron density analysis, topological analysis, Mulliken atomic charges, natural atomic charges and harmonic vibrational analysis. The geometrical parameters and vibrational frequencies of dmax (the mono anion of 1,3-dimethyl-8-azaxanthine), [M2+(H2O)6] (M = Mn, Ni, Co, Zn, Cd), [M2+(H2O)4·(py)2] (M = Mn, Co, Zn, Cd) and the complexes, calculated by the theoretical methods, were compared with the recent X-ray crystallographic results and it was observed that the results are found to agree well with the crystallographic results. The present calculations provide an important physicochemical insight into metal cations with 1,3-dimethyl-8-azaxanthine. The results also reveal the active role of coordinated water molecules in modulating the binding of the cation through a specific network of hydrogen bonds. The topology of the motifs generated by these hydrogen bonds has been characterized, adapting to the second coordination sphere concepts usually applied to the first (monodentate, chelate, and bridge) coordination sphere. The optimized structures of the Cd2+, Zn2+ and Cu2+ complexes further interact among themselves in a less tight fashion to generate three dimensional structures (a tape-like hydrogen bond network). Finally these tape-like hydrogen bond network were optimized using the B3LYP/LANL2DZ basis set.

The hydrogen bonding pattern in complexes of type [M2+(H2O)6](dmax)2 (M = Mn, Ni, Co, Zn, Cd, Hdmax = 1,3-dimethyl-8-azaxanthine), [M2+(H2O)4·(py)2](dmax)2 (M = Mn, Co, Zn, Cd, py = pyridine) and [M2+(dmax)2(H2O)2·(py)2]·2H2O (M = Ni, Cu) were studied by ab initio (MP2/LANL2DZ//B3LYP/LANL2DZ) and density functional theory methods (B3LYP/LANL2DZ, B3LYP/6-31G∗∗ and B3PW91/6-31G∗∗).Figure optionsDownload as PowerPoint slideHighlights
► Theoretical methods were compared with the recent X-ray crystallographic results.
► The binding of the cation through a specific network of hydrogen bonds.
► Tape like hydrogen bond network were optimized using B3LYP/ LANL2DZ basis set.