Cocrystallization of equimolar quantities of sulfathiazole (STL) with each of 1,4-diazabicyclo[2.2.2]octane (DABCO) and piperazine (PIP) resulted in facile formation of salts [DABCOH][STL_H] (1) and [PIPH][STL_H] (2), respectively. Crystallography shows the formation of aniline-N−H•••O (sulfonyl) hydrogen bonds between anions to form supramolecular undulating and zigzag layers, respectively, with the cations being connected to these by charge-assisted N−H•••N(thioazole) interactions. 1 H NMR, IR, and Raman spectroscopies as well as powder Xray diffraction (PXRD) and differential scanning calorimetry (DSC) confirmed salt formation. Solid state grinding competition experiments were monitored by PXRD. In a sequence of experiments where STL was coground with a molar equivalent of PIP and n equivalents of DABCO (with n increasing from 0.1 to 1.0 in 0.1 increments), preferential formation of 1 was observed. In related experiments where 2 was ground with an equimolar amount of DABCO, substitution of PIPH + by DABCOH + was evident; i.e., postsynthetic metathesis had occurred to about 70% for dry grinding. Quantitative yields were obtained in the case of liquid-assisted grinding (LAG) with a few drops of ethanol after 1.4 equiv of DABCO were added. These observations are primarily correlated with differences in aniline-N−H•••O(sulfonyl) hydrogen bonding that sustain the layers.
The dihedral angle between the benzene and pyridyl rings in the title compound, C11H8ClN3O2, is 22.65 (10)°, indicating a twisted molecule. The amine H and nitro O atoms form a donor–acceptor pair for an intramolecular N—H⋯O hydrogen bond so that the nitro group is almost coplanar with the pyridine ring to which it is connected [O—N—C—C torsion angle = 7.4 (3)°]. The pyridine N and Cl atoms are approximately syn. The crystal packing features C—H⋯Cl interactions that lead to undulating supramolecular chains along [101]. These are connected into sheets by π–π interactions occurring between the benzene rings and between the pyridine rings of translationally related molecules along the b axis [centroid–centroid distances = length of b axis = 3.7157 (2) Å].
The crystal and molecular structures of three ammonium salts derived from sulfathiazole are described. In each case, the anion is in the azanide form, features an intramolecular S←O interaction, and adopts a U-shape. The structures of two cations, [R(HOCH 2 CH 2 )NH 2 ] + , namely for R = Me (1) and iPr (2), are unprecedented in the crystallographic literature. Extensive hydrogen bonding is observed in all crystal structures and leads to a two-dimensional array for 1, and three-dimensional architectures for each of 2 and 3 (R = CH 2 CH 2 OH). The salts exhibited anti-microbial activity against a range of Gram-positive and Gram-negative bacteria, and proved bactericidal toward Vibrio parahaemolyticus, but had no advantage over sulfathiazole itself.
In the title compound, C11H8ClN3O2, the presence of intramolecular N—H⋯O and C—H⋯N interactions help to establish an almost planar molecule [dihedral angle between the pyridine and benzene rings = 9.89 (8)° and r.m.s. deviation for all 17 non-H atoms = 0.120 Å]. Supramolecular tapes feature in the crystal packing whereby dimeric aggregates sustained by pairs of C—H⋯O interactions are connected by π–π interactions occurring between translationally related pyridine rings and between translationally related benzene rings along the b axis [centroid–centroid distance = length of b axis = 3.8032 (4) Å].
Molecules in both polymorphs of the title compound display deviations from planarity owing to crystal packing effects.
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