
Web Release Date: October 19,
Pseudopolymorph: A Polemic
The QUILL Centre, The Queen's University of Belfast, United Kingdom, BT9 5AG
Received July 26, 2004
In a recent Letter,1 Gautam Desiraju argued two
rather controversial points. Primarily, he proclaimed his
discomfort with the term cocrystal (or co-crystal), probably first introduced, and certainly popularized, by the
late Margaret Etter:2,3
So, let us examine the meaning of the word pseudopolymorph. Taking Desiraju's own definition, polymorphism is "the phenomenon wherein the same substance exhibits different crystal packing arrangements".6 If we enlarge on this definition, polymorphism is the ability of a substance to adopt different internal structures and external forms, in response to different conditions of temperature and/or pressure and/or crystallization. Thus, a polymorph is the crystallographer's equivalent to a molecular isomer. For elements, polymorphism expresses itself as allotropy.7 It is central, and unequivocal, to the definition and understanding of polymorphism that different polymorphs have the same chemical and molecular composition, differing only in the way those molecules are packed in the lattice. The prefix pseudo- means false or spurious.8 Thus, a pseudopolymorph must be a false, or spurious, polymorph. In other words, it must be a material that apparently is a different crystalline form of a material, but in reality is not. Now, as there should never be any doubt, in this century, about the chemical identity of a material, then it follows that solvates of a compound can never be pseudopolymorphs, as there will never be any doubt as to their chemical identity. To draw a parallel in the art world, we could call a forgery of Van Gogh's "Sunflowers", if we so desired, a pseudo-"Sunflowers"-it would be false or spurious, and is similar enough to the original to be mistaken for it. But, we could not describe a fake "Mona Lisa" as a pseudo-"Sunflowers", despite being false, as there was never any possibility of mistaking one for the other.
So let us be clear. The term pseudopolymorph is now commonly being applied to mean the solvate, or (in the specific case of water) hydrate, of a material. We gain no new understanding by introducing the term "pseudopolymorphs", and indeed it is pedagogically misleading. It has been introduced into the literature, but I believe it should be expunged; editors should insist that it is removed from manuscripts in which it is used prior to publication. The term "solvate" has been around for centuries, is universally understood, and is a perfect descriptor for these materials. Why introduce unnecessary and misleading jargon?
* E-mail: k.seddon@qub.ac.uk.
1. Desiraju, G. R. CrystEngComm 2003, 5, 466-467.
2. Etter, M. C.; Panunto, T. W. J. Am. Chem. Soc. 1988, 110,
5896-5897.
3. Etter, M. C. J. Phys. Chem. 1991, 95, 4601-4610.
4. Dunitz, J. D. CrystEngComm 2003, 5, 506.
5. Rogers, R. D. Cryst. Growth Des. 2003, 3, 867.
6. Sarma, J. A. R. P.; Desiraju, G. R. In Crystal Engineering: The Design and Application of Functional Solids; Seddon, K. R., Zaworotko, M., Eds.; Kluwer: Dordrecht, 1999; Vol. 539, pp 325-356.
7. Seddon, K. R. In Crystal Engineering: The Design and Application of Functional Solids; Seddon, K. R., Zaworotko, M., Eds.; Kluwer: Dordrecht, 1999; Vol. 539, pp 1-28.
8. CD-ROM, Britannica DVD 2002 Expanded Edition; Encyclopædia Britannica Inc., Chicago, IL, 2002.