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Title: Solid-state chemistry of cyclic thiohydroxamic acids : prediction and measurement
Author: Bond, A. D.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2000
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In this thesis, the solid-state chemistry of a variety of closely-related cyclic thiohydroxamic acids is examined. Primarily, derivatives of two molecules are considered: 1-hydroxy-2(1H)-pyridinethione (PT) and 3-hydroxy-4-methyl-2(3H)-thiazolethione (MTT). Although less extensively studied to date, MTT is likely to exhibit antimicrobial activity similar to that of PT. The database of crystallographic information for organic PT and MTT derivatives, and their divalent complexes with zinc, copper, nickel and cobalt is expanded significantly. In addition to single-crystal X-ray diffraction using laboratory sources, several other techniques are employed for elucidation of the crystal structures. These include diffraction utilising synchrotron sources, and Rietveld refinement using laboratory powder X-ray diffraction data. Molecular-modelling procedures, including lattice-energy calculation and minimisation, are also employed extensively. Prediction of crystal structure on the basis of molecular information only is a particularly attractive prospect. It is shown in this thesis that existing methodology is adequate for prediction of the crystal structures of PT, MTT and their divalent complexes with zinc, copper and nickel. An extension to existing methodology for the treatment of general divalent complexes is proposed. Prediction in conjunction with Rietveld refinement is shown to be a viable strategy for determination of the crystal structures of divalent complexes. This may be of particular value where single crystals suitable for X-ray analysis cannot be obtained. The physicochemical properties of a molecular material are known to depend on both molecular and crystal structure. Modification of solid-state structure in a controlled manner may, therefore, provide materials with enhanced physicochemical properties. Strategies employed for structure modification in this thesis include the formation of hydrates and mixed crystals. A novel hydrate of zinc pyrithione with enhanced aqueous solubility is reported, and a mixed crystal incorporating zinc complexes of PT and MTT is also described.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available