Migrating hydrogen in 2,4,6-triaminopyrimidinium(1+)
 x
 hydrogen trioxofluorophosphate(−)
 x
 monohydrate/2,4,6-triaminopyrimidinium(2+)1–x
 trioxofluorophosphate(2–)1–x
 monohydrate (0.0 &lt; x &lt; 0.73) with changing temperature

Many efforts have been recently devoted to the design and investigation of multicomponent pharmaceutical solids, such as salts and cocrystals. The experimental distinction between these solid forms is often challenging. Here, we show that the transformation of a salt into a cocrystal with a short hydrogen bond does not occur as a sharp phase transition but rather a smooth shift of the positional probability of the hydrogen atoms. A combination of solid-state NMR spectroscopy, X-ray diffraction, and diffuse reflectance measurements with density functional theory calculations that include nuclear quantum effects (NQEs) provides evidence of temperature-induced hydrogen atom shift in cocrystals with short hydrogen bonds. We demonstrate that for the predictions of the salt/cocrystal solid forms with short H-bonds, the computations have to include NQEs (particularly hydrogen nuclei delocalization) and temperature effects.

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Isostructural Crystals of Bis(Guanidinium) Trioxofluoro-Phosphate/Phosphite in the Ratio 1/0, 0.716/0.284, 0.501/0.499, 0.268/0.732, 0/1—Crystal Structures, Vibrational Spectra and Second Harmonic Generation

Matulková

Fábry

Eigner

et al. 2022

Crystals

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The title structures of bis(guanidinium) trioxofluorophosphate, bis(guanidinium) trioxofluorophosphate-phosphite (0.716/0.284), bis(guanidinium) trioxofluorophosphate-phosphite (0.501/0.499), bis(guanidinium) trioxofluorophosphate-phosphite (0.268/0.732), and bis(guanidinium) phosphite are crystal-chemically isotypic. Their structures correspond to the structure of bis(guanidinium) trioxofluorophosphate which was determined by Prescott, Troyanov, Feist & Kemnitz (Z. Anorg. Allg. Chem. 2002, 628, 1749–1755). The P and O atoms of the substituted trioxofluorophosphate and phosphite anions share the same positions while the P-F and P-Hhydrido are almost parallel and oriented in the same direction. Two symmetry-independent anions and two of three symmetry-independent cations are situated on the crystallographic mirror planes. The ions are interconnected by N-H⋯O hydrogen bonds of moderate strength. The most frequent graph set motif is R22(8), which involves interactions between the primary amine groups and the trioxofluorophosphate or phosphite O atoms. Fluorine, as well as the hydrido hydrogen, avoids inclusion into the hydrogen-bond network. The Hirshfeld surface analysis was also performed for the comparison of intermolecular interactions in the title structures of bis(guanidinium trioxofluorophosphate and bis(guanidinium) phosphite. The title crystals were also characterized by vibrational spectroscopy methods (FTIR and FT Raman) and the second harmonic generation (SHG). The relative SHG efficiency considerably decreases from bis(guanidinium) trioxofluorophosphate to bis(guanidinium) phosphite for the fundamental 1064 nm laser line.

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Migrating hydrogen in 2,4,6-triaminopyrimidinium(1+)_x hydrogen trioxofluorophosphate(−)_x monohydrate/2,4,6-triaminopyrimidinium(2+)_1–x trioxofluorophosphate(2–)_1–x monohydrate (0.0 < x < 0.73) with changing temperature

Abstract: Edited by E. V. Boldyreva, Russian Academy of Sciences, Russia

Cited by 3 publications

References 42 publications

The hydrogen bond continuum in solid isonicotinic acid

The hydrogen bond continuum in solid isonicotinic acid

Importance of Nuclear Quantum Effects for Molecular Cocrystals with Short Hydrogen Bonds

Isostructural Crystals of Bis(Guanidinium) Trioxofluoro-Phosphate/Phosphite in the Ratio 1/0, 0.716/0.284, 0.501/0.499, 0.268/0.732, 0/1—Crystal Structures, Vibrational Spectra and Second Harmonic Generation

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Migrating hydrogen in 2,4,6-triaminopyrimidinium(1+) x hydrogen trioxofluorophosphate(−) x monohydrate/2,4,6-triaminopyrimidinium(2+)1–x trioxofluorophosphate(2–)1–x monohydrate (0.0 < x < 0.73) with changing temperature

Abstract: Edited by E. V. Boldyreva, Russian Academy of Sciences, Russia

Cited by 3 publications

References 42 publications

The hydrogen bond continuum in solid isonicotinic acid

The hydrogen bond continuum in solid isonicotinic acid

Importance of Nuclear Quantum Effects for Molecular Cocrystals with Short Hydrogen Bonds

Isostructural Crystals of Bis(Guanidinium) Trioxofluoro-Phosphate/Phosphite in the Ratio 1/0, 0.716/0.284, 0.501/0.499, 0.268/0.732, 0/1—Crystal Structures, Vibrational Spectra and Second Harmonic Generation

Contact Info

Product

Resources

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Migrating hydrogen in 2,4,6-triaminopyrimidinium(1+)_x hydrogen trioxofluorophosphate(−)_x monohydrate/2,4,6-triaminopyrimidinium(2+)_1–x trioxofluorophosphate(2–)_1–x monohydrate (0.0 < x < 0.73) with changing temperature