Hydrogen-bonded mol­ecular salts of reduced benzo­thia­zole derivatives with carboxyl­ates: a robust [R_{2}^{2}](8) supra­molecular motif (even when disordered)

Shaibah, Mohammed A. E. and Sagar, B. K. and Yathirajan, H. S. and Cordes, David B. and Slawin, Alexandra M. Z. and Harrison, William T. A. (2019) Hydrogen-bonded mol­ecular salts of reduced benzo­thia­zole derivatives with carboxyl­ates: a robust [R_{2}^{2}](8) supra­molecular motif (even when disordered). Acta Crystallographica Section E, 75 (2). pp. 167-174. ISSN 1600-5368

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Official URL: https://doi.org/10.1107/S2056989018018224


The syntheses and structures of five mol­ecular salts of protonated 4,4,7,7-tetra­methyl-3a,5,6,7a-tetra­hydro­benzo­thia­zol-2-yl­amine (C11H19N2S+) with different deprotonated carb­oxy­lic acids (4-methyl­benzoic acid, 4-bromo­benzoic acid, 3,5-di­nitro­benzoic acid, fumaric acid and succinic acid) are reported, namely 2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium 4-methyl­benzoate, C11H19N2S+·C8H7O2−, (I), 2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium 4-bromo­benzoate, C11H19N2S+·C7H4BrO2−, (II), 2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium 3,5-di­nitro­benzoate, C11H19N2S+·C7H3N2O6−, (III), bis­(2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium) fumarate, 2C11H19N2S+·C4H2O42−,(IV), and the 1:1 co-crystal of bis­(2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium) succinate and 2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium hydrogen succin­ate 4,4,7,7-tetra­methyl-3a,5,6,7a-tetra­hydro­benzo­thia­zol-2-yl­amine, 1.5C11H19N2S+·0.5C4H4O42−·0.5C4H5O4−. 0.5C11H18N2S, (V). In every case, the cation protonation occurs at the N atom of the thia­zole ring and the six-membered ring adopts a half-chair conformation (in some cases, the deviating methyl­ene groups are disordered over two sets of sites). The C—N bond lengths of the nominal –NH+=C—NH2 fragment of the cation are indistinguishable, indicating a significant contribution of the –NH—C=N+H2 resonance form to the structure. The packing for (I)–(V) features a robust local R22(8) loop motif in which the cation forms two near-linear N—H⋯O hydrogen bonds from the N+—H group and syn H atom of the amine group to the carboxyl­ate group of an adjacent anion [(V) shows disorder of one of these bonds over N—H⋯O and N⋯H—O contributors but the same R22(8) loop results for both disorder components]. The anti H atom of the –NH2 group also forms an N—H⋯O hydrogen bond, which results in [001] chains in (I) and (II), isolated centrosymmetric tetra­mers in (III) and [100] chains in (IV) and (V). Hirshfeld fingerprint plots and contact percentages for the different types of contacts of the cations are discussed.

Item Type: Article
Uncontrolled Keywords: benzothiazole, hydrogen bond, molecular salt, crystal structure
Subjects: C Chemical Science > Chemistry
Divisions: Department of > Chemistry
Depositing User: C Swapna Library Assistant
Date Deposited: 12 Oct 2019 10:30
Last Modified: 12 Oct 2019 10:30
URI: http://eprints.uni-mysore.ac.in/id/eprint/8947

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