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. 2016 Sep 23;72(Pt 10):1456-1459.
doi: 10.1107/S2056989016014298. eCollection 2016 Oct 1.

Hydrogen bonding, π-π stacking and van der Waals forces-dominated layered regions in the crystal structure of 4-amino-pyridinium hydrogen (9-phosphono-non-yl)phospho-nate

Martin van Megen  1 , Guido J Reiss  1 , Walter Frank  1
Affiliations

Hydrogen bonding, π-π stacking and van der Waals forces-dominated layered regions in the crystal structure of 4-amino-pyridinium hydrogen (9-phosphono-non-yl)phospho-nate

Martin van Megen et al. Acta Crystallogr E Crystallogr Commun. .

Abstract

The asymmetric unit of the title mol-ecular salt, [C5H7N2+][(HO)2OP(CH2)9PO2(OH)-], consists of one 4-amino-pyridinium cation and one hydrogen (9-phos-phono-non-yl)phospho-nate anion, both in general positions. As expected, the 4-amino-pyridinium moieties are protonated exclusively at their endocyclic nitro-gen atom due to a mesomeric stabilization by the imine form which would not be given in the corresponding double-protonated dicationic species. In the crystal, the phosphonyl (-PO3H2) and hydrogen phospho-nate (-PO3H) groups of the anions form two-dimensional O-H⋯O hydrogen-bonded networks in the ab plane built from 24-membered hydrogen-bonded ring motifs with the graph-set descriptor R66(24). These networks are pairwise linked by the anions' alkyl-ene chains. The 4-amino-pyridinium cations are stacked in parallel displaced face-to-face arrangements and connect neighboring anionic substructures via medium-strong charge-supported N-H⋯O hydrogen bonds along the c axis. The resulting three-dimensional hydrogen-bonded network shows clearly separated hydro-philic and hydro-phobic structural domains.

Keywords: 4-amino­pyridinium; bis­(phospho­nate); crystal structure; hydrogen bonding.

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Figures

Figure 1
Figure 1
The asymmetric unit of the title compound plus symmetry-related hydrogen-bonded atoms [displacement ellipsoids are drawn at the 50% probability level; hydrogen atoms are drawn as spheres with arbitrary radii; symmetry codes: (i) 1 + x, −1 + y, 1 + z; (ii) x, −1 + y, 1 + z; (iii) 1 − x, 2 − y, 1 − z; (iv) 1 − x, 1 − y, 1 − z; (v) −x, 1 − y, 1 − z; (vi) −1 + x, 1 + y, −1 + z, (vii) x, 1 + y, −1 + z].
Figure 2
Figure 2
Two-dimensional hydrogen-bonded networks composed of phosphonyl and hydrogen phospho­nate groups. The graph set formula image(24) is indicated by blue bonds.
Figure 3
Figure 3
View along [010] of the title structure, showing the hydrogen bonding (red), π–π stacking (blue), and van der Waals forces (grey) dominated layered regions within the three-dimensional network.
Figure 4
Figure 4
The IR (blue) and Raman (red) spectra of the title compound.
See this image and copyright information in PMC

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