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Chemical Insights from Systematic Structural Studies. The ‘Stamp Collecting’ Approach to Understanding the Solid State

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Crystallizing Ideas – The Role of Chemistry

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Abstract

Many industries, most notably pharmaceutical, have for some time been using compound libraries as a systematic approach to comprehensively understanding a chemical landscape. Screening in medicinal chemistry is an obvious example and Quantitative Structure Activity Relationship (QSAR) takes a similar, in silico, approach. Understanding packing and structure-determining factors in the solid state is key in many areas, e.g. polymorphism or crystallisation, and of course we need to understand this behaviour if we are to control solid-state formation in any way. It is therefore rather surprising that there are relatively few systematic studies being conducted on the solid state in the way we now routinely work in these other areas. This paper presents numerous systematic studies of homologous series of compounds that have been studied as ‘libraries’ in the solid state—sometimes these families of related compounds can have as many as 200–300 crystal structures. Results that enable us to derive rules and begin to predict solid-state behaviour will be presented. Taking this concept further, some series of ultra-high resolution structural families are presented—from these studies a comparison of electron density distributions leads to very detailed correlations between bonding and reactivity. Finally, in order not only to rationalise the large amounts of data generated, but also to begin to analyse for prediction purposes, a concept for a statistical approach to describe and build models of crystal structures is outlined.

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Acknowledgements

This article contains, and alludes to, a summary of a vast amount of work—it is most certainly not solely down to the author! Firstly, I would like to acknowledge the Engineering and Physical Sciences Research Council for its continued funding of the UK National Crystallography Service over a period spanning more than three decades (and has directly funded the author for two of these!). My mentor, Mike Hursthouse, introduced me to this entire subject area and did the majority of the founding work—and is continuing to do so with just as much insight from retirement. Terry Threlfall has a wealth of experience in this area—he began collaborating with the group around 20 years ago and is still driving us forward with as much enthusiasm and insight as ever. The researchers who conduct the work, past and present, are numerous and involve a wide range of people from summer students through to retired professors. The most notable, who directly contributed to the specific work described herein, are Graham Tizzard, Mateusz Pitak, Claire Wilson, Thomas Gelbrich, Philip Adler, Isabelle Kirby, Riccardo Montis, Amy Ellis, Jonathan Sarson, Ka Leung and Eleanor Dodd.

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Authors and Affiliations

  1. Department of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK

    Simon J. Coles

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  1. Simon J. Coles
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Correspondence to Simon J. Coles .

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Editors and Affiliations

  1. Dep. of Chemistry, Fac. of Science, University of Mauritius, Reduit, Mauritius

    Ponnadurai Ramasami

  2. Dept of Chemistry, Faculty of Scien, University of Mauritius, Reduit, Mauritius

    Minu Gupta Bhowon

  3. Dept. of Chemistry, Faculty of Scie, University of Mauritius, Reduit, Mauritius

    Sabina Jhaumeer Laulloo

  4. Reduit, Mauritius

    Henri Li Kam Wah

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Coles, S.J. (2016). Chemical Insights from Systematic Structural Studies. The ‘Stamp Collecting’ Approach to Understanding the Solid State. In: Ramasami, P., Gupta Bhowon, M., Jhaumeer Laulloo, S., Li Kam Wah, H. (eds) Crystallizing Ideas – The Role of Chemistry. Springer, Cham. https://doi.org/10.1007/978-3-319-31759-5_1

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