Crystal Structure of the Chiral Azomethine Imine, (Z)-(S)-4-(tert-Butylcarbonylamino)-2-(2-methoxybenzylidene)-5-oxopyrazolidin-2-ium-1-ide, Obtained by the Cyclization of tert-Butyl (S)-2-[2-(methoxybenzylidene)hydrazine]-1-(hydroxymethyl)-2-oxocarbamate

Alessandra C. Pinheiro, Marcus V. N. de Souza, Solange M. S. V. Wardell, James L. Wardell (Corresponding Author)

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Abstract

Further study of the cyclization reactions of (S)-t-BuOCH2CONHCH(CH2OH)CONHN = Ar, derived from (l)-serine, has found that reaction with MeI/K2CO3 in Me2CO produces (Z)-(S)-4-(tert-butylcarbonylamino)-2-(benzylidene)-5-oxopyrazolidin-2-ium-1-ide, 3. We now wish to report the crystal structure of the 2-methoxybenzylidene derivative, 3a. While the pyrazolyl ring in 3a exhibits an envelope shape, with the flap at C5, the displacement of C5 from the best plane through the ring, however, is only 0.053(5) Å. The dihedral angle between the phenyl and pyrazolyl rings is 12.14(16)°. The pyrazolyl ring has a betaine character with opposite charges on N1 and N2 atoms. The supramolecular arrangement is created from one classical N–H···O and weaker C–H···X (X = O, N) intermolecular hydrogen bonds, each of which generate chains of molecules. Combinations of the (i) C19–H19A···O1 and C11–H11···O2 hydrogen bonds generates sheets of molecules in the ab plane, containing R44(40) rings, (ii) C18–H18B···O1 and C11–H11···O2 hydrogen bonds produce a two molecule wide column, containing R33(26) rings, propagated in the ac plane and (iii) C19–H19A···O1 and C15–H15A···N2 hydrogen bonds generate a different two molecule wide column, containing R33(26) rings, propagated in the ab plane. The compound crystallises in the orthorhombic space group, P212121, with a = 6.5906(5) Å, b = 10.9121(10) Å, c = 22.2080(17) Å, and Z = 4.


Original languageEnglish
JournalJournal of Chemical Crystallography
Early online date15 Nov 2018
DOIs
Publication statusE-pub ahead of print - 15 Nov 2018

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hydrazine
Imines
Cyclization
hydrazines
imines
Hydrogen
Hydrogen bonds
Crystal structure
crystal structure
Molecules
rings
hydrogen bonds
Betaine
Dihedral angle
molecules
Serine
betaines
Derivatives
Atoms
azomethine

Keywords

  • Azomethine imines
  • Cyclization reactions
  • Serine derivative
  • Hydrogen bonds

Cite this

@article{8bfb44f3a65c44e19534b0cc824813af,
title = "Crystal Structure of the Chiral Azomethine Imine, (Z)-(S)-4-(tert-Butylcarbonylamino)-2-(2-methoxybenzylidene)-5-oxopyrazolidin-2-ium-1-ide, Obtained by the Cyclization of tert-Butyl (S)-2-[2-(methoxybenzylidene)hydrazine]-1-(hydroxymethyl)-2-oxocarbamate",
abstract = "Further study of the cyclization reactions of (S)-t-BuOCH2CONHCH(CH2OH)CONHN = Ar, derived from (l)-serine, has found that reaction with MeI/K2CO3 in Me2CO produces (Z)-(S)-4-(tert-butylcarbonylamino)-2-(benzylidene)-5-oxopyrazolidin-2-ium-1-ide, 3. We now wish to report the crystal structure of the 2-methoxybenzylidene derivative, 3a. While the pyrazolyl ring in 3a exhibits an envelope shape, with the flap at C5, the displacement of C5 from the best plane through the ring, however, is only 0.053(5) {\AA}. The dihedral angle between the phenyl and pyrazolyl rings is 12.14(16)°. The pyrazolyl ring has a betaine character with opposite charges on N1 and N2 atoms. The supramolecular arrangement is created from one classical N–H···O and weaker C–H···X (X = O, N) intermolecular hydrogen bonds, each of which generate chains of molecules. Combinations of the (i) C19–H19A···O1 and C11–H11···O2 hydrogen bonds generates sheets of molecules in the ab plane, containing R44(40) rings, (ii) C18–H18B···O1 and C11–H11···O2 hydrogen bonds produce a two molecule wide column, containing R33(26) rings, propagated in the ac plane and (iii) C19–H19A···O1 and C15–H15A···N2 hydrogen bonds generate a different two molecule wide column, containing R33(26) rings, propagated in the ab plane. The compound crystallises in the orthorhombic space group, P212121, with a = 6.5906(5) {\AA}, b = 10.9121(10) {\AA}, c = 22.2080(17) {\AA}, and Z = 4.",
keywords = "Azomethine imines, Cyclization reactions, Serine derivative, Hydrogen bonds",
author = "Pinheiro, {Alessandra C.} and {de Souza}, {Marcus V. N.} and Wardell, {Solange M. S. V.} and Wardell, {James L.}",
note = "Open Access via Springer Compact Agreement. Funded by CNPQ.",
year = "2018",
month = "11",
day = "15",
doi = "10.1007{\%}2Fs10870-018-0751-1",
language = "English",
journal = "Journal of Chemical Crystallography",
issn = "1074-1542",
publisher = "Springer New York",

}

TY - JOUR

T1 - Crystal Structure of the Chiral Azomethine Imine, (Z)-(S)-4-(tert-Butylcarbonylamino)-2-(2-methoxybenzylidene)-5-oxopyrazolidin-2-ium-1-ide, Obtained by the Cyclization of tert-Butyl (S)-2-[2-(methoxybenzylidene)hydrazine]-1-(hydroxymethyl)-2-oxocarbamate

AU - Pinheiro, Alessandra C.

AU - de Souza, Marcus V. N.

AU - Wardell, Solange M. S. V.

AU - Wardell, James L.

N1 - Open Access via Springer Compact Agreement. Funded by CNPQ.

PY - 2018/11/15

Y1 - 2018/11/15

N2 - Further study of the cyclization reactions of (S)-t-BuOCH2CONHCH(CH2OH)CONHN = Ar, derived from (l)-serine, has found that reaction with MeI/K2CO3 in Me2CO produces (Z)-(S)-4-(tert-butylcarbonylamino)-2-(benzylidene)-5-oxopyrazolidin-2-ium-1-ide, 3. We now wish to report the crystal structure of the 2-methoxybenzylidene derivative, 3a. While the pyrazolyl ring in 3a exhibits an envelope shape, with the flap at C5, the displacement of C5 from the best plane through the ring, however, is only 0.053(5) Å. The dihedral angle between the phenyl and pyrazolyl rings is 12.14(16)°. The pyrazolyl ring has a betaine character with opposite charges on N1 and N2 atoms. The supramolecular arrangement is created from one classical N–H···O and weaker C–H···X (X = O, N) intermolecular hydrogen bonds, each of which generate chains of molecules. Combinations of the (i) C19–H19A···O1 and C11–H11···O2 hydrogen bonds generates sheets of molecules in the ab plane, containing R44(40) rings, (ii) C18–H18B···O1 and C11–H11···O2 hydrogen bonds produce a two molecule wide column, containing R33(26) rings, propagated in the ac plane and (iii) C19–H19A···O1 and C15–H15A···N2 hydrogen bonds generate a different two molecule wide column, containing R33(26) rings, propagated in the ab plane. The compound crystallises in the orthorhombic space group, P212121, with a = 6.5906(5) Å, b = 10.9121(10) Å, c = 22.2080(17) Å, and Z = 4.

AB - Further study of the cyclization reactions of (S)-t-BuOCH2CONHCH(CH2OH)CONHN = Ar, derived from (l)-serine, has found that reaction with MeI/K2CO3 in Me2CO produces (Z)-(S)-4-(tert-butylcarbonylamino)-2-(benzylidene)-5-oxopyrazolidin-2-ium-1-ide, 3. We now wish to report the crystal structure of the 2-methoxybenzylidene derivative, 3a. While the pyrazolyl ring in 3a exhibits an envelope shape, with the flap at C5, the displacement of C5 from the best plane through the ring, however, is only 0.053(5) Å. The dihedral angle between the phenyl and pyrazolyl rings is 12.14(16)°. The pyrazolyl ring has a betaine character with opposite charges on N1 and N2 atoms. The supramolecular arrangement is created from one classical N–H···O and weaker C–H···X (X = O, N) intermolecular hydrogen bonds, each of which generate chains of molecules. Combinations of the (i) C19–H19A···O1 and C11–H11···O2 hydrogen bonds generates sheets of molecules in the ab plane, containing R44(40) rings, (ii) C18–H18B···O1 and C11–H11···O2 hydrogen bonds produce a two molecule wide column, containing R33(26) rings, propagated in the ac plane and (iii) C19–H19A···O1 and C15–H15A···N2 hydrogen bonds generate a different two molecule wide column, containing R33(26) rings, propagated in the ab plane. The compound crystallises in the orthorhombic space group, P212121, with a = 6.5906(5) Å, b = 10.9121(10) Å, c = 22.2080(17) Å, and Z = 4.

KW - Azomethine imines

KW - Cyclization reactions

KW - Serine derivative

KW - Hydrogen bonds

U2 - 10.1007%2Fs10870-018-0751-1

DO - 10.1007%2Fs10870-018-0751-1

M3 - Article

JO - Journal of Chemical Crystallography

JF - Journal of Chemical Crystallography

SN - 1074-1542

ER -