Issue 4, 2010

High-pressure polymorphism in salicylamide


We report the compression of a single crystal of salicylamide to 5.1 GPa. Between ambient pressure and 5.1 GPa the structure remains in a compressed form of the ambient-pressure phase, referred to as salicylamide-I. This phase has been investigated twice previously, but the coordinates appear to have been reported with respect to a non-standard space group origin, though no comment to this effect is made in either of the original reports. Short H⋯H contacts implied by the previously published coordinates are strongly destabilising according to PIXEL packing energy calculations, but are absent in the structure reported here. A new high-pressure polymorph, salicylamide-II, is formed if salicylamide is crystallised in situ from a saturated solution in a 4 : 1 mixture of methanol and ethanol at 0.2 GPa. Crystal growth yielded three crystallites within the pressure cell, and combination of single-crystal X-ray diffraction intensity data from all three yielded a dataset which was >90% complete. PIXEL calculations indicate that salicylamide-II exhibits weaker H-bonding but stronger dispersion interactions than phase-I. Harmonic frequencies calculated using periodic DFT (and validated by inelastic neutron scattering data) indicate that phase-II is favoured at high pressure by its lower volume, its lower zero-point energy and higher entropy, and we estimate that at 0.2 GPa the free energy of phase-II is lower than that of phase-I by about 3 kJ mol−1.

Graphical abstract: High-pressure polymorphism in salicylamide

Supplementary files

Article information

Article type
13 Oct 2009
11 Dec 2009
First published
20 Jan 2010

CrystEngComm, 2010,12, 1065-1078

High-pressure polymorphism in salicylamide

R. D. L. Johnstone, A. R. Lennie, S. F. Parker, S. Parsons, E. Pidcock, P. R. Richardson, J. E. Warren and P. A. Wood, CrystEngComm, 2010, 12, 1065 DOI: 10.1039/B921288D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity