Hydrogen Bonded Supramolecular Association in Organic Acid–Base Salts: Crystal Structures of Four Proton-Transfer Complexes Assembled from 2-Amino-4-methylpyridine with 2-Chloro, 4-Chloro, 3-Methyl and 4-Methylbenzoic Acid

The crystal structures of the 1:2 compounds of chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) with 2-pyridone, 3-hydroxypyridine and 4-hyroxypyridine, namely, bis(2-pyridone) chloranilic acid, 2C5H5NO·C6H2Cl2O4, (I), bis(3-hydroxypyridinium) chloranilate, 2C5H6NO+·C6Cl2O42−, (II), and bis(4-hydroxypyridinium) chloranilate, 2C5H6NO+·C6Cl2O42−, (III), have been determined at 120 K. In the crystal of (I), the base molecule is in the lactam form and no acid–base interaction involving H-atom transfer is observed. The acid molecule lies on an inversion centre and the asymmetric unit consists of one half-molecule of chloranilic acid and one 2-pyridone molecule, which are linkedviaa short O—H...O hydrogen bond. 2-Pyridone molecules form a head-to-head dimerviaa pair of N—H...O hydrogen bonds, resulting in a tape structure along [201]. In the crystals of (II) and (III), acid–base interactions involving H-atom transfer are observed and the divalent cations lie on an inversion centre. The asymmetric unit of (II) consists of one half of a chloranilate anion and one 3-hydroxypyridinium cation, while that of (III) comprises two independent halves of anions and two 4-hydroxypyridinium cations. The primary intermolecular interaction in (II) is a bifurcated O—H...(O,O) hydrogen bond between the cation and the anion. The hydrogen-bonded units are further linkedviaN—H...O hydrogen bonds, forming a layer parallel to thebcplane. In (III), one anion is surrounded by four cationsviaO—H...O and C—H...O hydrogen bonds, while the other is surrounded by four cationsviaN—H...O and C—H...Cl hydrogen bonds. These interactions link the cations and the anions into a layer parallel to (301).

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Hydrogen-bonded Supramolecular Association in Organic Acid-base Pyrimidine Salt and Hirshfeld Surface Analysis

Journal of Physics Conference Series ◽

10.1088/1742-6596/1083/1/012048 ◽

2018 ◽

Vol 1083 ◽

pp. 012048

Author(s):

Nuridayanti Che Khalib ◽

Kaliyaperumal Thanigaimani ◽

Suhana Arshad ◽

Dian Alwani Zainuri ◽

Ibrahim Abdul Razak

Keyword(s):

Organic Acid ◽

Surface Analysis ◽

Hirshfeld Surface ◽

Hirshfeld Surface Analysis ◽

Acid Base ◽

Hydrogen Bonded

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A solid-state oxidation of 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfinate to 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfonate

Acta Crystallographica Section C Crystal Structure Communications ◽

10.1107/s0108270113015011 ◽

2013 ◽

Vol 69 (7) ◽

pp. 778-780 ◽

Cited By ~ 2

Author(s):

Åsmund Kaupang ◽

Carl Henrik Görbitz ◽

Tore Bonge-Hansen

Keyword(s):

Solid State ◽

Hydrogen Bonds ◽

Organic Acid ◽

Crystal Structures ◽

Monoclinic Space Group ◽

Acid Base ◽

Space Group ◽

Base Complex ◽

Oxidation In Air

The organic acid–base complex 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfonate, C5H14N3+·C7H7O3S−, was obtained from the corresponding 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfinate complex, C5H14N3+·C7H7O2S−, by solid-state oxidation in air. Comparison of the two crystal structures reveals similar packing arrangements in the monoclinic space groupP21/c, with centrosymmetric 2:2 tetramers being connected by four strong N—H...O=S hydrogen bonds between the imine N atoms of two 1,1,3,3-tetramethylguanidinium bases and the O atoms of two acid molecules.

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