The effect of pressure and temperature on the vibrational spectra of different hydrogen bonded systems

The effect of pressure and temperature on the vibrational spectra of hydrogen bonded systems has been studied on amides, thioamides, carboxylic acids and urea. The compounds under investigation are indicative for the kind of hydrogen bonding changing from pure intermolecular to intramolecular and dimeric forms. The discussion of the temperature dependence on the fundamentals involved in the hydrogen bonding is straightforward but the pressure data are much more complicated and only if the changes in the crystalline state at different pressures are known, we will have a better understanding of the dependence of some fundamentals in the hydrogen bonded systems. A clear example of this approach is given for urea.     

Hydrogen-bonded networks based on manganese(II), nickel(II), copper(II) and zinc(II) complexes of N,N′-dimethylurea

A project related to the crystal engineering of hydrogen-bonded coordination complexes has been initiatied and some of our first results are presented here. The compounds [Mn(DMU)₆](ClO₄)₂ (1), [Ni(DMU)₆](ClO₄)₂ (2), [Cu(OClO₃)₂(DMU)₄] (3) and [Zn(DMU)₆](ClO₄)₂ (4) have all been prepared from the reaction of N,N-dimethylurea (DMU) and the appropriate hydrated metal perchlorate salt. Crystal structure determinations of the four compounds demonstrate the existence of [M(DMU)₆]²⁺ cations and ClO₄ ^– counterions in (1), (2) and (4), whereas in (3) monodentate coordination of the perchlorate groups leads to molecules. The [M(DMU)₆]²⁺ cations and ClO₄ ^– anions self-assemble to form a hydrogen-bonded one-dimensional (1D) architecture in (1) and different 2D hydrogen-bonded networks in (2) and (4). The hydrogen bonding functionalities on the molecules of (3) create a 2D structure. The complexes were also characterised by room-temperature effective magnetic moments and i.r. studies. The data are discussed in terms of the nature of bonding and the known structures.     

A structural model for the copper(II) site of Cu-Zn superoxide dismutase: preparation,crystal structure and properties of [Cu(Mebta)4(H2O)](ClO4)2·0.4EtOH (Mebta = 1-methylbenzotriazole)

Reaction of Cu(ClO₄)₂·6H₂O with 1-methylbenzotriazole (Mebta) in EtOH yields [Cu(Mebta)₄(H₂O)] (ClO₄)₂·0.4EtOH in ca. 75% yield. The structure of this salt has been determined by single-crystal X-ray crystallography. Mebta behaves as a monodentate ligand binding through N(3). The metal coordination geometry is best described as distorted square pyramidal with the H₂O ligand occupying the apical site. The complex was also characterized by molar conductivity, room-temperature effective magnetic moment and spectroscopic (i.r., far-i.r., u.v./vis, e.s.r.) studies. The data are discussed in terms of the nature of bonding and known structure. Comparison between the structural and spectroscopic properties of [Cu(Mebta)₄(H₂O)](ClO₄)₂·0.4EtOH and those of the Cu^II site of Cu–Zn superoxide dismutase shows that the former can be considered as a fairly good model for the latter.