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Experimental and Theoretical Investigation of Structures, Stoichiometric Diversity, and Bench Stability of Cocrystals with a Volatile Halogen Bond Donor
journal contribution
posted on 2018-02-27, 00:00 authored by Katarina Lisac, Vinko Nemec, Filip Topić, Mihails Arhangelskis, Poppy Hindle, Ricky Tran, Igor Huskić, Andrew J. Morris, Tomislav Friščić, Dominik CinčićWe
present a combined experimental and theoretical study of the
structures and bench stability of halogen-bonded cocrystals involving
the volatile halogen bond donor octafluoro-1,4-diiodobutane, with
phenazine and acridine as acceptors. Cocrystallization experiments
using mechanochemistry and solution crystallization revealed three
chemically and structurally distinct cocrystals. Whereas only one
cocrystal form has been observed with acridine, cocrystallization
with phenazine led to two stoichiometrically different cocrystals,
in which phenazine employs either one or two nitrogen atoms per molecule
as halogen bond acceptor sites. Cocrystal stability was evaluated
experimentally by simultaneous thermogravimetric analysis and differential
thermal analysis or differential scanning calorimetry, real-time powder
X-ray diffraction monitoring of cocrystals upon storage in open air,
and theoretically by using dispersion-corrected periodic density functional
theory. The use of real-time powder X-ray diffraction enabled the
comparison of rates of cocrystal decomposition, and the observed trends
in cocrystal stability were reproduced by the ranking of theoretically
calculated cocrystal decomposition enthalpies. Whereas all cocrystals
eventually lose the volatile halogen bond donor upon storage in open
air or by heating, these experimental and theoretical studies show
that the cocrystal of acridine is the most stable, in agreement with
its more basic properties. The stoichiometric variations of the phenazine
cocrystal also exhibit a notable difference in stability, with the
cocrystal containing the halogen bond acceptor and donor in a 1:1
stoichiometric ratio being of particularly low stability, decomposing
in open air within minutes.
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thermogravimetric analysispowder X-ray diffractioncocrystal stabilitycocrystal decomposition enthalpiescocrystal formhalogen bond acceptor sitescocrystal decompositionstoichiometric variationshalogen bond donorpowder X-ray diffraction monitoringCocrystal stabilitynitrogen atomsTheoretical Investigationscanning calorimetryhalogen bond acceptorphenazine cocrystalsolution crystallizationCocrystallization experimentsstudies showbench stabilityhalogen-bonded cocrystalsVolatile Halogen Bond DonorBench StabilityStoichiometric Diversity
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