Influence of lattice interactions on the jahn-teller distortion of the [Cu(H2O)(6)](2+) ion: Dependence of the crystal structure of K-2[Cu(H2O)(6)](SO4)(2x)(SeO4)(2-2x) upon the sulfate/selenate ratio

The temperature dependence of the structure of the mixed-anion Tutton salt K-2[Cu(H2O)(6)](SO4)(2x)(SeO4)(2-2x) has been determined for crystals with 0, 17, 25, 68, 78, and 100% sulfate over the temperature range of 85-320 K. In every case, the [Cu(H2O)(6)](2+) ion adopts a tetragonally elongated coordination geometry with an orthorhombic distortion. However, for the compounds with 0, 17, and 25% sulfate, the long and intermediate bonds occur on a different pair of water molecules from those with 68, 78, and 100% sulfate. A thermal equilibrium between the two forms is observed for each crystal, with this developing more readily as the proportions of the two counterions become more similar. Attempts to prepare a crystal with approximately equal amounts of sulfate and selenate were unsuccessful. The temperature dependence of the bond lengths has been analyzed using a model in which the Jahn-Teller potential surface of the [Cu(H2O)(6)](2+) ion is perturbed by a lattice-strain interaction. The magnitude and sign of the orthorhombic component of this strain interaction depends on the proportion of sulfate to selenate. Significant deviations from Boltzmann statistics are observed for those crystals exhibiting a large temperature dependence of the average bond lengths, and this may be explained by cooperative interactions between neighboring complexes.

Polyamines from polyols - Pathways to azamacrocycles with hydroxymethyl pendent groups

Several pathways to macromonocylic polyamine ligands with pendent hydroxymethyl substituents have been explored. The new ligands have all been characterised by single-crystal, X-ray structure determinations on their complexes with Co(III) (one case) and Cu(II). As in some related systems, four-membered ring species, here oxetanes rather than azetidines, appear to be involved as reaction intermediates and can be quite readily isolated, providing reactants of potential for the construction of even more complicated multidentate ligands. (C) 2005 Elsevier Ltd. All rights reserved.

Edge-to-edge matching and its applications - Part II. Application to Mg-Al, Mg-Y and Mg-Mn alloys

A model for the crystallography and morphology of diffusion-controlled phase transformations - edge-to-edge matching - has been used to predict the orientation relationships (OR) and habit planes of precipitates Mg17Al12 in Mg-Al alloy, Mg24Y5 in Mg-Y alloy and alpha-Mn in Mg-Mn alloy. Based on the crystal structures and lattice parameters only, the model predicts that the possible ORs between Mg17Al12 and Mg matrix are the near Burgers OR, the Potter OR, the Gjonnes-Ostmoe OR and the Crawley OR. In the Mg-Y alloy, the OR between Mg24Y5 precipitates and the Mg matrix is predicted to be the Burgers OR only. The model also predicts that there are no reproducible ORs between alpha-Mn and Mg in the Mg-Mn alloy. Combining the edge-to-edge matching model and W. Zhang's Deltag approach, the habit plane and side facets of the precipitate for each OR can be determined. All the predicted ORs and the corresponding habit planes in Mg-Al and Mg-Y alloys agree very well with the experimental results. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.