2,2′,2″-Thiotris(acetic acid) betaine, S(CH 2 COOH) 2 (CH 2 COO), and 2,2′,2″-selenotris(acetic acid) betaine, Se(CH 2 COOH) 2 (CH 2 COO)

Khalid Doudin*, Karl Törnroos

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

TThe title compounds, X(CH2COOH)2(CH2COO), X = S, 1, and X = Se, 2, have been characterised by FTIR, NMR and MS and by their crystal structures at 123(2) K. The FTIR spectra show two major peaks, at 1396 and 1731 cm−1 in 1 and at 1390 and 1721 cm−1 in 2. The 77Se NMR signal of 2 at 325.5 ppm is 83.4 ppm downfield from the signal of Se(CH2COOH)2 indicating a substantial selenonium character of 2. The two compounds are isostructural and have a pyramidal configuration. The C—X—C bond angles range from 99.29 to 103.14° in 1 and from 97.56 to 99.87° in 2. The Xsingle bondCsingle bondCdouble bond; length as m-dashO torsion angles for the three substituents are most different; one of the carboxylic acid groups attains the anti-conformation with rather short S⋯O(H) and Se⋯O(H) distances, 2.744 and 2.750 Å, the other acid group is synclinal and with longer S⋯Odouble bond; length as m-dashC and Se⋯Odouble bond; length as m-dashC distances, 3.063 and 3.090 Å, whereas the carboxylate group is in the Xsingle bondCsingle bondC plane with X⋯Osingle bondC distances of 2.869 and 2.908 Å in 1 and 2. The presence of these strong X⋯O interactions is suggested to be the cause for the very low Bronsted basicity of this class of betaines preventing salts of the corresponding acids, the presently unknown [X(CH2COOH)3]+ - cations, to be isolated. The molecules are linked together with two fairly strong but different hydrogen bonds to the carboxylate oxygen atoms with O⋯O distances of 2.493 and 2.580 Å in 1 and 2.489 and 2.581 Å in 2 and with one X⋯Odouble bond; length as m-dashC contact, 3.244 Å in 1 and 3.209 Å in 2. The carbonyl oxygen atoms do not participate significantly in intermolecular hydrogen bonding and there are no contacts between the heteroatoms.
Original languageEnglish
Pages (from-to)611–616
Number of pages6
JournalJournal of Molecular Structure
Volume1134
Early online date7 Jan 2017
DOIs
Publication statusPublished - 15 Apr 2017

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Betaine
Acetic Acid
Hydrogen bonds
Nuclear magnetic resonance
Oxygen
Atoms
Acids
Alkalinity
Carboxylic Acids
Torsional stress
Conformations
Cations
Salts
Crystal structure
Molecules
carboxyl radical

Bibliographical note

© 2017, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/

Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/10.1016/j.molstruc.2016.12.067. These data include MOL files and InChiKeys of the most important compounds described in this article.

Keywords

  • selenium betaine
  • sulphur betaine
  • 77Se NMR
  • crystal structures
  • MS
  • FTIR

Cite this

@article{f084ddff27c5458d958145202095c231,
title = "2,2′,2″-Thiotris(acetic acid) betaine, S(CH 2 COOH) 2 (CH 2 COO), and 2,2′,2″-selenotris(acetic acid) betaine, Se(CH 2 COOH) 2 (CH 2 COO)",
abstract = "TThe title compounds, X(CH2COOH)2(CH2COO), X = S, 1, and X = Se, 2, have been characterised by FTIR, NMR and MS and by their crystal structures at 123(2) K. The FTIR spectra show two major peaks, at 1396 and 1731 cm−1 in 1 and at 1390 and 1721 cm−1 in 2. The 77Se NMR signal of 2 at 325.5 ppm is 83.4 ppm downfield from the signal of Se(CH2COOH)2 indicating a substantial selenonium character of 2. The two compounds are isostructural and have a pyramidal configuration. The C—X—C bond angles range from 99.29 to 103.14° in 1 and from 97.56 to 99.87° in 2. The Xsingle bondCsingle bondCdouble bond; length as m-dashO torsion angles for the three substituents are most different; one of the carboxylic acid groups attains the anti-conformation with rather short S⋯O(H) and Se⋯O(H) distances, 2.744 and 2.750 {\AA}, the other acid group is synclinal and with longer S⋯Odouble bond; length as m-dashC and Se⋯Odouble bond; length as m-dashC distances, 3.063 and 3.090 {\AA}, whereas the carboxylate group is in the Xsingle bondCsingle bondC plane with X⋯Osingle bondC distances of 2.869 and 2.908 {\AA} in 1 and 2. The presence of these strong X⋯O interactions is suggested to be the cause for the very low Bronsted basicity of this class of betaines preventing salts of the corresponding acids, the presently unknown [X(CH2COOH)3]+ - cations, to be isolated. The molecules are linked together with two fairly strong but different hydrogen bonds to the carboxylate oxygen atoms with O⋯O distances of 2.493 and 2.580 {\AA} in 1 and 2.489 and 2.581 {\AA} in 2 and with one X⋯Odouble bond; length as m-dashC contact, 3.244 {\AA} in 1 and 3.209 {\AA} in 2. The carbonyl oxygen atoms do not participate significantly in intermolecular hydrogen bonding and there are no contacts between the heteroatoms.",
keywords = "selenium betaine, sulphur betaine, 77Se NMR, crystal structures, MS, FTIR",
author = "Khalid Doudin and Karl T{\"o}rnroos",
note = "{\circledC} 2017, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/10.1016/j.molstruc.2016.12.067. These data include MOL files and InChiKeys of the most important compounds described in this article.",
year = "2017",
month = "4",
day = "15",
doi = "10.1016/j.molstruc.2016.12.067",
language = "English",
volume = "1134",
pages = "611–616",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
publisher = "Elsevier",

}

TY - JOUR

T1 - 2,2′,2″-Thiotris(acetic acid) betaine, S(CH 2 COOH) 2 (CH 2 COO), and 2,2′,2″-selenotris(acetic acid) betaine, Se(CH 2 COOH) 2 (CH 2 COO)

AU - Doudin, Khalid

AU - Törnroos, Karl

N1 - © 2017, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/10.1016/j.molstruc.2016.12.067. These data include MOL files and InChiKeys of the most important compounds described in this article.

PY - 2017/4/15

Y1 - 2017/4/15

N2 - TThe title compounds, X(CH2COOH)2(CH2COO), X = S, 1, and X = Se, 2, have been characterised by FTIR, NMR and MS and by their crystal structures at 123(2) K. The FTIR spectra show two major peaks, at 1396 and 1731 cm−1 in 1 and at 1390 and 1721 cm−1 in 2. The 77Se NMR signal of 2 at 325.5 ppm is 83.4 ppm downfield from the signal of Se(CH2COOH)2 indicating a substantial selenonium character of 2. The two compounds are isostructural and have a pyramidal configuration. The C—X—C bond angles range from 99.29 to 103.14° in 1 and from 97.56 to 99.87° in 2. The Xsingle bondCsingle bondCdouble bond; length as m-dashO torsion angles for the three substituents are most different; one of the carboxylic acid groups attains the anti-conformation with rather short S⋯O(H) and Se⋯O(H) distances, 2.744 and 2.750 Å, the other acid group is synclinal and with longer S⋯Odouble bond; length as m-dashC and Se⋯Odouble bond; length as m-dashC distances, 3.063 and 3.090 Å, whereas the carboxylate group is in the Xsingle bondCsingle bondC plane with X⋯Osingle bondC distances of 2.869 and 2.908 Å in 1 and 2. The presence of these strong X⋯O interactions is suggested to be the cause for the very low Bronsted basicity of this class of betaines preventing salts of the corresponding acids, the presently unknown [X(CH2COOH)3]+ - cations, to be isolated. The molecules are linked together with two fairly strong but different hydrogen bonds to the carboxylate oxygen atoms with O⋯O distances of 2.493 and 2.580 Å in 1 and 2.489 and 2.581 Å in 2 and with one X⋯Odouble bond; length as m-dashC contact, 3.244 Å in 1 and 3.209 Å in 2. The carbonyl oxygen atoms do not participate significantly in intermolecular hydrogen bonding and there are no contacts between the heteroatoms.

AB - TThe title compounds, X(CH2COOH)2(CH2COO), X = S, 1, and X = Se, 2, have been characterised by FTIR, NMR and MS and by their crystal structures at 123(2) K. The FTIR spectra show two major peaks, at 1396 and 1731 cm−1 in 1 and at 1390 and 1721 cm−1 in 2. The 77Se NMR signal of 2 at 325.5 ppm is 83.4 ppm downfield from the signal of Se(CH2COOH)2 indicating a substantial selenonium character of 2. The two compounds are isostructural and have a pyramidal configuration. The C—X—C bond angles range from 99.29 to 103.14° in 1 and from 97.56 to 99.87° in 2. The Xsingle bondCsingle bondCdouble bond; length as m-dashO torsion angles for the three substituents are most different; one of the carboxylic acid groups attains the anti-conformation with rather short S⋯O(H) and Se⋯O(H) distances, 2.744 and 2.750 Å, the other acid group is synclinal and with longer S⋯Odouble bond; length as m-dashC and Se⋯Odouble bond; length as m-dashC distances, 3.063 and 3.090 Å, whereas the carboxylate group is in the Xsingle bondCsingle bondC plane with X⋯Osingle bondC distances of 2.869 and 2.908 Å in 1 and 2. The presence of these strong X⋯O interactions is suggested to be the cause for the very low Bronsted basicity of this class of betaines preventing salts of the corresponding acids, the presently unknown [X(CH2COOH)3]+ - cations, to be isolated. The molecules are linked together with two fairly strong but different hydrogen bonds to the carboxylate oxygen atoms with O⋯O distances of 2.493 and 2.580 Å in 1 and 2.489 and 2.581 Å in 2 and with one X⋯Odouble bond; length as m-dashC contact, 3.244 Å in 1 and 3.209 Å in 2. The carbonyl oxygen atoms do not participate significantly in intermolecular hydrogen bonding and there are no contacts between the heteroatoms.

KW - selenium betaine

KW - sulphur betaine

KW - 77Se NMR

KW - crystal structures

KW - MS

KW - FTIR

UR - http://www.scopus.com/inward/record.url?scp=85009085089&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2016.12.067

DO - 10.1016/j.molstruc.2016.12.067

M3 - Article

VL - 1134

SP - 611

EP - 616

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

ER -