Expected and unexpected products of reactions of 2-hydrazinylbenzothiazole with 3-nitrobenzenesulfonyl chloride in different solvents

Alexandra Morscher, Marcus V. N. de Souza, James Wardell, William T. A. Harrison

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Abstract

The syntheses and crystal structures of 2-[2-(propan-2-yl­idene)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C10H12N2S+·C6H4NO5S−), (I), 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zole (C13H10N4O4S2), (II) and 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C13H11N4O4S2+·C6H4NO5S−), (III) are reported. Salt (I) arose from an unexpected reaction of 2-hydrazinylbenzo­thia­zole with the acetone solvent in the presence of 3-nitro­benzene­sulfonyl chloride, whereas (II) and (III) were recovered from the equivalent reaction carried out in methanol. The crystal of (I) features ion pairs linked by pairs of N—H...Os (s = sulfonate) hydrogen bonds; adjacent cations inter­act by way of short π–π stacking inter­actions between the thia­zole rings [centroid–centroid separation = 3.4274 (18) Å]. In (II), which crystallizes with two neutral mol­ecules in the asymmetric unit, the mol­ecules are linked by N—H...N and N—H...On (n = nitro) hydrogen bonds to generate [\overline{1}1\overline{1}] chains, which are cross-linked by C—H...O and π–π stacking inter­actions. The crystal of (III) features centrosymmetric tetra­mers (two cations and two anions) linked by cooperative N—H...O hydrogen bonds; C—H...O and π–π inter­actions occur between tetra­mers.
Original languageEnglish
Pages (from-to)673-677
Number of pages5
JournalActa Crystallographica Section E: Crystallographic Communications
Volume74
Issue number5
Early online date17 Apr 2018
DOIs
Publication statusPublished - May 2018

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Chlorides
Hydrogen bonds
chlorides
hydrogen bonds
Cations
products
Positive ions
methylidyne
Thiazoles
cations
Crystals
Molecules
interactions
Acetone
sulfonates
acetone
crystals
Anions
Methanol
molecules

Keywords

  • crystal structure
  • hydrazinylbenzothiazole
  • hydrogen bonds
  • molecular salt

Cite this

@article{b2e2f34b389545e9a829fe26d2863669,
title = "Expected and unexpected products of reactions of 2-hydrazinylbenzothiazole with 3-nitrobenzenesulfonyl chloride in different solvents",
abstract = "The syntheses and crystal structures of 2-[2-(propan-2-yl­idene)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C10H12N2S+·C6H4NO5S−), (I), 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zole (C13H10N4O4S2), (II) and 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C13H11N4O4S2+·C6H4NO5S−), (III) are reported. Salt (I) arose from an unexpected reaction of 2-hydrazinylbenzo­thia­zole with the acetone solvent in the presence of 3-nitro­benzene­sulfonyl chloride, whereas (II) and (III) were recovered from the equivalent reaction carried out in methanol. The crystal of (I) features ion pairs linked by pairs of N—H...Os (s = sulfonate) hydrogen bonds; adjacent cations inter­act by way of short π–π stacking inter­actions between the thia­zole rings [centroid–centroid separation = 3.4274 (18) {\AA}]. In (II), which crystallizes with two neutral mol­ecules in the asymmetric unit, the mol­ecules are linked by N—H...N and N—H...On (n = nitro) hydrogen bonds to generate [\overline{1}1\overline{1}] chains, which are cross-linked by C—H...O and π–π stacking inter­actions. The crystal of (III) features centrosymmetric tetra­mers (two cations and two anions) linked by cooperative N—H...O hydrogen bonds; C—H...O and π–π inter­actions occur between tetra­mers.",
keywords = "crystal structure, hydrazinylbenzothiazole, hydrogen bonds, molecular salt",
author = "Alexandra Morscher and {de Souza}, {Marcus V. N.} and James Wardell and Harrison, {William T. A.}",
note = "Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the X-ray data collections. Funding information MVNdS and JLW thank CNPq (Brazil) for financial support.",
year = "2018",
month = "5",
doi = "10.1107/S2056989018005595",
language = "English",
volume = "74",
pages = "673--677",
journal = "Acta Crystallographica Section E: Crystallographic Communications",
issn = "2056-9890",
publisher = "International Union of Crystallography",
number = "5",

}

TY - JOUR

T1 - Expected and unexpected products of reactions of 2-hydrazinylbenzothiazole with 3-nitrobenzenesulfonyl chloride in different solvents

AU - Morscher, Alexandra

AU - de Souza, Marcus V. N.

AU - Wardell, James

AU - Harrison, William T. A.

N1 - Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the X-ray data collections. Funding information MVNdS and JLW thank CNPq (Brazil) for financial support.

PY - 2018/5

Y1 - 2018/5

N2 - The syntheses and crystal structures of 2-[2-(propan-2-yl­idene)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C10H12N2S+·C6H4NO5S−), (I), 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zole (C13H10N4O4S2), (II) and 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C13H11N4O4S2+·C6H4NO5S−), (III) are reported. Salt (I) arose from an unexpected reaction of 2-hydrazinylbenzo­thia­zole with the acetone solvent in the presence of 3-nitro­benzene­sulfonyl chloride, whereas (II) and (III) were recovered from the equivalent reaction carried out in methanol. The crystal of (I) features ion pairs linked by pairs of N—H...Os (s = sulfonate) hydrogen bonds; adjacent cations inter­act by way of short π–π stacking inter­actions between the thia­zole rings [centroid–centroid separation = 3.4274 (18) Å]. In (II), which crystallizes with two neutral mol­ecules in the asymmetric unit, the mol­ecules are linked by N—H...N and N—H...On (n = nitro) hydrogen bonds to generate [\overline{1}1\overline{1}] chains, which are cross-linked by C—H...O and π–π stacking inter­actions. The crystal of (III) features centrosymmetric tetra­mers (two cations and two anions) linked by cooperative N—H...O hydrogen bonds; C—H...O and π–π inter­actions occur between tetra­mers.

AB - The syntheses and crystal structures of 2-[2-(propan-2-yl­idene)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C10H12N2S+·C6H4NO5S−), (I), 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zole (C13H10N4O4S2), (II) and 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C13H11N4O4S2+·C6H4NO5S−), (III) are reported. Salt (I) arose from an unexpected reaction of 2-hydrazinylbenzo­thia­zole with the acetone solvent in the presence of 3-nitro­benzene­sulfonyl chloride, whereas (II) and (III) were recovered from the equivalent reaction carried out in methanol. The crystal of (I) features ion pairs linked by pairs of N—H...Os (s = sulfonate) hydrogen bonds; adjacent cations inter­act by way of short π–π stacking inter­actions between the thia­zole rings [centroid–centroid separation = 3.4274 (18) Å]. In (II), which crystallizes with two neutral mol­ecules in the asymmetric unit, the mol­ecules are linked by N—H...N and N—H...On (n = nitro) hydrogen bonds to generate [\overline{1}1\overline{1}] chains, which are cross-linked by C—H...O and π–π stacking inter­actions. The crystal of (III) features centrosymmetric tetra­mers (two cations and two anions) linked by cooperative N—H...O hydrogen bonds; C—H...O and π–π inter­actions occur between tetra­mers.

KW - crystal structure

KW - hydrazinylbenzothiazole

KW - hydrogen bonds

KW - molecular salt

U2 - 10.1107/S2056989018005595

DO - 10.1107/S2056989018005595

M3 - Article

VL - 74

SP - 673

EP - 677

JO - Acta Crystallographica Section E: Crystallographic Communications

JF - Acta Crystallographica Section E: Crystallographic Communications

SN - 2056-9890

IS - 5

ER -