The effect of temperature on the crystal structure of deuterated piperidine has been studied using neutron powder diffraction. Differential scanning calorimetry indicates that there are multiple phases accessible via changes in temperature however there is no evidence of this in the neutron powder diffraction study with only one phase observed in the range 2 – 250 K and under various crystallisation conditions. The effect of pressure up to 2.79 GPa has also been determined. The compression of the structure is facilitated through the closing up of voids in the structure and no phase transition is observed. Differential scanning calorimetry has shown N-methyl and N,N-dimethylformamide both exhibit a thermal event prior to melting. Low temperature neutron powder diffraction has shown these transitions are associated with the onset of methyl group rotation. Neutron powder diffraction studies show formamide exhibits remarkable polymorphism at ambient temperature and pressures between 0.1 GPa and 3.6 GPa, forming four new polymorphs. All the structures consist of N-H…O hydrogen bonded chains. The formation of the various polymorphs can be rationalised in terms of the orientation of the molecules within the hydrogen bonded chains and the resultant structures formed by further hydrogen bonds between the chains. This is in stark contrast to the effect of varying conditions of temperature where only one structure exists from 2 K right up to the melting point. The effect of temperature on the crystal structure of pyrazine in the range 8 – 315 K is described. At temperatures below 90 K the structure undergoes a phase transition to a previously uncharacterised phase, designated phase IV, which is closely related to the previously known phase I. The crystal structure of phase III has been determined at 315 K. The crystal structure of pyrazine has been determined at room temperature at pressures between 0.11 GPa and 9.36 GPa. At 0.94 GPa a transition from phase I to phase IV is observed. This is the same phase as observed at low temperatures. Crystal growth at 215 K results in the formation of two different phases of mesitylene; phase II and a new previously unknown phase designated phase IV. The structure of phase IV has been determined and found to be stable in the range 90 – 221 K. On cooling a crystal of deuterated mesitylene in phase II to 90 K a transition to phase III was observed and the resultant crystal structure is closely related to that of phase II.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:562820 |
| Date | January 2010 |
| Creators | Budd, Laura Elizabeth |
| Contributors | Parsons, Simon. : Ibberson, Richard |
| Publisher | University of Edinburgh |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/1842/3967 |
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