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 (Corresponding Author)

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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 (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.
Original languageEnglish
Pages (from-to)167-174
Number of pages8
JournalActa Crystallographica Section E: Crystallographic Communications
Volume75
Issue number2
Early online date8 Jan 2019
DOIs
Publication statusPublished - 1 Feb 2019

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carboxylates
Cations
Bromobenzoates
Hydrogen
Succinic Acid
Salts
salts
Derivatives
acids
Positive ions
Acids
hydrogen
cations
Atoms
Hydrogen bonds
Thiazoles
Fumarates
disorders
Protonation
hydrogen bonds

Keywords

  • benzothiazole
  • hydrogen bond
  • molecular salt
  • crystal structure

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Chemistry(all)
  • Materials Science(all)

Cite this

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.; Sagar, Belakavadi K.; Yathirajan, Hemmige S.; Cordes, David B.; Slawin, Alexandra M. Z.; Harrison, William T. A. (Corresponding Author).

In: Acta Crystallographica Section E: Crystallographic Communications, Vol. 75, No. 2, 01.02.2019, p. 167-174.

Research output: Contribution to journalArticle

Shaibah, Mohammed A. E. ; Sagar, Belakavadi K. ; Yathirajan, Hemmige S. ; Cordes, David B. ; Slawin, Alexandra M. Z. ; Harrison, William T. A. / Hydrogen-bonded molecular salts of reduced benzothiazole derivatives with carboxylates : a robust R_2^2(8) supramolecular motif (even when disordered). In: Acta Crystallographica Section E: Crystallographic Communications. 2019 ; Vol. 75, No. 2. pp. 167-174.
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title = "Hydrogen-bonded molecular salts of reduced benzothiazole derivatives with carboxylates: a robust R_2^2(8) supramolecular motif (even when disordered)",
abstract = "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.",
keywords = "benzothiazole, hydrogen bond, molecular salt, crystal structure",
author = "Shaibah, {Mohammed A. E.} and Sagar, {Belakavadi K.} and Yathirajan, {Hemmige S.} and Cordes, {David B.} and Slawin, {Alexandra M. Z.} and Harrison, {William T. A.}",
note = "Acknowledgements MAES thanks the University of Mysore for provision of research facilities. Funding information 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.",
year = "2019",
month = "2",
day = "1",
doi = "10.1107/S2056989018018224",
language = "English",
volume = "75",
pages = "167--174",
journal = "Acta Crystallographica Section E: Crystallographic Communications",
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TY - JOUR

T1 - Hydrogen-bonded molecular salts of reduced benzothiazole derivatives with carboxylates

T2 - a robust R_2^2(8) supramolecular motif (even when disordered)

AU - Shaibah, Mohammed A. E.

AU - Sagar, Belakavadi K.

AU - Yathirajan, Hemmige S.

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Harrison, William T. A.

N1 - Acknowledgements MAES thanks the University of Mysore for provision of research facilities. Funding information 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.

PY - 2019/2/1

Y1 - 2019/2/1

N2 - 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.

AB - 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.

KW - benzothiazole

KW - hydrogen bond

KW - molecular salt

KW - crystal structure

UR - http://www.scopus.com/inward/record.url?scp=85061157335&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/hydrogenbonded-molecular-salts-reduced-benzothiazole-derivatives-carboxylates-robust-8-supramolecula

U2 - 10.1107/S2056989018018224

DO - 10.1107/S2056989018018224

M3 - Article

VL - 75

SP - 167

EP - 174

JO - Acta Crystallographica Section E: Crystallographic Communications

JF - Acta Crystallographica Section E: Crystallographic Communications

SN - 2056-9890

IS - 2

ER -