title: Absorbing a Little Water: The Structural, Thermodynamic, and Kinetic Relationship between Pyrogallol and Its Tetarto-Hydrate.
abstract: The anhydrate and the stoichiometric tetarto-hydrate of pyrogallol (0.25 mol water per mol pyrogallol) are both storage stable at ambient conditions, provided that they are phase pure, with the system being at equilibrium ataw(water activity) = 0.15 at 25 °C. Structures have been derived from single crystal and powder X-ray diffraction data for the anhydrate and hydrate, respectively. It is notable that the tetarto-hydrate forms a tetragonal structure with water in channels, a framework that although stabilized by water, is found as a higher energy structure on a computationally generated crystal energy landscape, which has the anhydrate crystal structure as the most stable form. Thus, a combination of slurry experiments, X-ray diffraction, spectroscopy, moisture (de)sorption, and thermo-analytical methods with the computationally generated crystal energy landscape and lattice energy calculations provides a consistent picture of the finely balanced hydration behavior of pyrogallol. In addition, two monotropically related dimethyl sulfoxide monosolvates were found in the accompanying solid form screen.
authors.affiliation: Institute of Pharmacy, University of Innsbruck , Innrain 52c, 6020 Innsbruck, Austria ; Department of Chemistry, University College London , 20 Gordon Street, London WC1H 0AJ, U.K.
authors.forename: Doris E
authors.initials: DE
authors.lastname: Braun
authors.forename: Rajni M
authors.initials: RM
authors.lastname: Bhardwaj
authors.forename: Jean-Baptiste
authors.initials: JB
authors.lastname: Arlin
authors.forename: Alastair J
authors.initials: AJ
authors.lastname: Florence
authors.forename: Volker
authors.initials: V
authors.lastname: Kahlenberg
authors.forename: Ulrich J
authors.initials: UJ
authors.lastname: Griesser
authors.forename: Derek A
authors.initials: DA
authors.lastname: Tocher
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Price
references.citation: Cryst Growth Des. 2013 Jan 2;13(1):19-23
references.pmid: 23378823
references.citation: Acc Chem Res. 2009 Jan 20;42(1):117-26
references.pmid: 18925751
references.citation: Chem Commun (Camb). 2011 May 21;47(19):5443-5
references.pmid: 21475750
references.citation: Cryst Growth Des. 2011 Jan 5;11(1):210-220
references.pmid: 21218174
references.citation: J Comput Chem. 2005 Feb;26(3):304-24
references.pmid: 15622548
references.citation: Chem Commun (Camb). 2011 Jul 7;47(25):7074-6
references.pmid: 21614395
references.citation: Phys Rev Lett. 2009 Feb 20;102(7):073005
references.pmid: 19257665
references.citation: Angew Chem Int Ed Engl. 1999 Dec 3;38(23):3440-3461
references.pmid: 10602208
references.citation: Phys Rev Lett. 1996 Oct 28;77(18):3865-3868
references.pmid: 10062328
references.citation: J Chem Phys. 2012 Sep 28;137(12):120901
references.pmid: 23020317
references.citation: Chem Soc Rev. 2009 Sep;38(9):2622-33
references.pmid: 19690742
references.citation: J Chem Phys. 2008 Jun 28;128(24):244708
references.pmid: 18601366
references.citation: Adv Drug Deliv Rev. 2001 May 16;48(1):3-26
references.pmid: 11325474
references.citation: Int J Pharm. 2011 Oct 14;418(2):168-78
references.pmid: 21497184
references.citation: Acta Crystallogr B. 2002 Jun;58(Pt 3 Pt 1):380-8
references.pmid: 12037359
references.citation: J Chem Theory Comput. 2008 Oct 14;4(10):1795-805
references.pmid: 26620182
references.citation: Cryst Growth Des. 2020 Sep 2;20(9):6069-6083
references.pmid: 32913424
references.citation: J Am Chem Soc. 2005 Apr 20;127(15):5512-7
references.pmid: 15826189
references.citation: Acta Crystallogr A. 2001 Jan;57(Pt 1):47-54
references.pmid: 11124502
references.citation: J Chem Phys. 2012 Aug 14;137(6):064506
references.pmid: 22897292
references.citation: Chemistry. 2009 Dec 7;15(47):13033-40
references.pmid: 19876969
references.citation: J Chem Theory Comput. 2011 Jun 14;7(6):1998-2016
references.pmid: 26596459
references.citation: Phys Chem Chem Phys. 2010 Aug 14;12(30):8478-90
references.pmid: 20607186
references.citation: Acta Crystallogr B. 2000 Jun;56 (Pt 3):526-34
references.pmid: 10877361
references.citation: Acta Crystallogr B. 2010 Oct;66(Pt 5):544-58
references.pmid: 20841921
references.citation: Phys Rev B Condens Matter. 1990 Apr 15;41(11):7892-7895
references.pmid: 9993096
references.citation: J Chem Theory Comput. 2005 Nov;1(6):1128-32
references.pmid: 26631656
references.citation: Eur J Pharm Biopharm. 2009 Jan;71(1):23-37
references.pmid: 18715549
references.citation: Phys Chem Chem Phys. 2008 Apr 21;10(15):1996-2009
references.pmid: 18688351
references.citation: Drug Discov Today. 2008 Mar;13(5-6):198-210
references.pmid: 18342795
references.citation: Acta Crystallogr A. 2008 Jan;64(Pt 1):112-22
references.pmid: 18156677
references.citation: J Pharm Sci. 1978 Sep;67(9):1338-9
references.pmid: 690852
references.citation: J Phys Chem B. 2012 Apr 5;116(13):3961-72
references.pmid: 22390190
references.citation: J Pharm Sci. 2007 Dec;96(12):3419-31
references.pmid: 17621678
references.citation: Angew Chem Int Ed Engl. 2007;46(4):615-7
references.pmid: 17131435