Diffuse scattering study of aspirin forms (I) and (II)

• Published in: Acta crystallographica. Section B, Structural science Vol. 66; no. 6; pp. 696 - 707
• Main Authors: Chan, E. J., Welberry, T. R., Heerdegen, A. P., Goossens, D. J.
• Format: Journal Article
• Language: English
• Published: 5 Abbey Square, Chester, Cheshire CH1 2HU, England International Union of Crystallography 01.12.2010; Blackwell Publishing Ltd
• Subjects: Aspirin; Aspirin - chemistry; Computer Simulation; Crystallization; Crystallography; Crystals; diffuse scattering; Diffusion; harmonic model; Models, Molecular; Molecular Conformation; Monte Carlo Method; Phase Transition; polymorphism; Research Papers; Scattering; Temperature
• ISSN: 0108-7681; 2052-5192; 1600-5740; 1600-5740; 2052-5206
• DOI: 10.1107/S0108768110037055

Full three‐dimensional diffuse scattering data have been recorded for both polymorphic forms [(I) and (II)] of aspirin and these data have been analysed using Monte Carlo computer modelling. The observed scattering in form (I) is well reproduced by a simple harmonic model of thermally induced displacements. The data for form (II) show, in addition to thermal diffuse scattering (TDS) similar to that in form (I), diffuse streaks originating from stacking fault‐like defects as well as other effects that can be attributed to strain induced by these defects. The present study has provided strong evidence that the aspirin form (II) structure is a true polymorph with a structure quite distinct from that of form (I). The diffuse scattering evidence presented shows that crystals of form (II) are essentially composed of large single domains of the form (II) lattice with a relatively small volume fraction of intrinsic planar defects or faults comprising misoriented bilayers of molecular dimers. There is evidence of some local aggregation of these defect bilayers to form small included regions of the form (I) structure. Evidence is also presented that shows that the strain effects arise from the mismatch of molecular packing between the defect region and the surrounding form (II) lattice. This occurs at the edges of the planar defects in the direction only.