Pressure-Promoted Solvation of Resorcinol.

Fatemeh Safari,Andrzej Katrusiak,Anna Olejniczak

doi:10.1021/acs.cgd.9b01732

Fatemeh Safari, Andrzej Katrusiak + Show 1 more

Open Access

https://doi.org/10.1021/acs.cgd.9b01732

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Abstract

Under ambient conditions resorcinol (Res), C6H4(OH)2, favorably crystallizes from methanol and aqueous solutions as the anhydrate, in the form of polymorph α at room temperature. Anhydrous polymorph β can be obtained above 360 K. However, above 0.80 GPa the monohydrate Res·H2O is formed from the aqueous solution. The monohydrate is less stable than the duotritohydrate 3Res·2H2O, which nucleates later. The latter forms a tight passivation layer on the surface of monohydrate crystals and protects them from dissolution. Between 0.20 and 1.0 GPa the duotritohydrate is more favored than the previously reported Res polymorphs α and β. From a methanol solution above 0.40 GPa the methanol monosolvate Res·CH3OH precipitates. In Res·H2O resorcinol molecules assume the syn-syn conformation, and in 3Res·2H2O independent syn-syn and anti-anti conformers are present. The anti-anti molecule is orientationally disordered, despite the fact that usually the disorder requires extra space, while the high pressure suppresses the volume. In all three new solvates, the solvent molecules mediate the H bonding between the hydroxyl groups. The formation of solvates can be rationalized by the low potential energy of syn-syn conformers as well as the volume gain of the solvates in comparison to the summed volumes of the pure resorcinol crystal and stoichiometric amounts of the solvent. The strong preference of the analogous orcinol (5-methylresorcinol) for the monohydrate formation under normal conditions is unchanged under high pressure.

Highlights

Pure compounds and their solvates and cocrystals can significantly differ in their physical and chemical properties
We have found that high pressure favors the formation of new solvates, which are unstable under ambient conditions
These new forms are resorcinol monohydrate, duotritohydrate, and monomethanol solvates. The stability of these new solvates at high pressure can be associated with the formation of new H bonds and with a volume gain of the solvates in comparison to the summed volume of their components

Summary

■ INTRODUCTION

Pure compounds and their solvates and cocrystals can significantly differ in their physical and chemical properties. We have investigated the preferences of resorcinol and orcinol (Figure 1) for crystallization as either the pure or solvated compounds under high pressure. Our present study is aimed at determining the thermodynamic preferences of resorcinol solvates and to form an understanding of the mechanisms favoring the formation of solvates at high pressure. Under standard conditions orcinol favorably forms a monohydrate and dry solvents are required to obtain the anhydrate (two polymorphs of pure orcinol are known).[45] our present study is aimed at understanding the strong preference of resorcinol to form the anhydrate. Recrystallizations from methanol and aqueous solutions in the DAC yielded new forms of resorcinol, as either polymorph α or β, up to 0.5 GPa. presently we have established that the pressure efficiently induces the formation of hydrates and a methanol solvate of resorcinol. The CIFs can be requested free of charge from https://www.ccdc.cam.ac.uk

■ DISCUSSION

■ CONCLUSIONS

■ REFERENCES