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

Mohammed A. E. Shaibah, Belakavadi K. Sagar, Hemmige S. Yathirajan, David B. Cordes, Alexandra M. Z. Slawin, William T. A. Harrison

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Abstract

The syntheses and structures of five mol­ecular salts of protonated 4,4,7,7-tetra­methyl-3a,5,6,7a-tetra­hydro­benzo­thia­zol-2-yl­amine (C11H 19N 2S +) 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, C11H 19N 2S +·C 8H 7O 2 , (I), 2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium 4-bromo­benzoate, C11H 19N 2S +·C 7H 4BrO 2 , (II), 2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium 3,5-di­nitro­benzoate, C11H 19N 2S +·C 7H 3N 2O 6 , (III), bis­(2-amino-4,4,7,7-tetra­methyl-4,5,6,7-tetra­hydro-1,3-benzo­thia­zol-3-ium) fumarate, 2C11H 19N 2S +·C 4H 2O 4 2−,(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, 1.5C11H 19N 2S +·0.5C 4H 4O 4 2−·0.5C 4H 5O 4 . 0.5C11H 18N 2S, (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—NH 2 fragment of the cation are indistinguishable, indicating a significant contribution of the –NH—C=N+H 2 resonance form to the structure. The packing for (I)–(V) features a robust local R 2 2(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 R 2 2(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.
Original languageEnglish
Pages (from-to)167-174
Number of pages8
JournalActa Crystallographica Section E
Volume75
Issue number2
DOIs
Publication statusPublished - 1 Feb 2019

Keywords

  • Benzothiazole
  • Hydrogen bond
  • Molecular salt
  • Crystal structure

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