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

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Date
01/02/2019
Author
Shaibah, Mohammed A. E.
Sagar, Belakavadi K.
Yathirajan, Hemmige S.
Cordes, David B.
Slawin, Alexandra M. Z.
Harrison, William T. A.
Keywords
Benzothiazole
Hydrogen bond
Molecular salt
Crystal structure
QD Chemistry
DAS
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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.
Citation
Shaibah , M A E , Sagar , B K , Yathirajan , H S , Cordes , D B , Slawin , A M Z & Harrison , W 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 , vol. 75 , no. 2 , pp. 167-174 . https://doi.org/10.1107/S2056989018018224
Publication
Acta Crystallographica Section E
Status
Peer reviewed
DOI
https://doi.org/10.1107/S2056989018018224
ISSN
2056-9890
Type
Journal article
Rights
Copyright © 2019 The Author(s). This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Description
HSY thanks UGC for the award of a UGC–BSR Faculty Fellowship for three years. BKS thanks the UGC for the award of a Rajeev Gandhi fellowship.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/17069

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