The influence of cation upon the supramolecular aggregation patterns of dithiocarbamate anions functionalised with hydrogen bonding capacity - The prevalence of charge-assisted O-H⋯S interactions

R. Alan Howie, Geraldo M. De Lima, Daniele C. Menezes, James L. Wardell, Solange M.S.V. Wardell, David J. Young, Edward R.T. Tiekink

Research output: Contribution to journalArticleResearchpeer-review

Abstract

A range of supramolecular architectures is found in the title dithiocarbamate salts, each with hydrogen bonding functionality in the form of aτ least one hydroxyl group. A common feature in the crystal packing is the prevalence of charge-assisted O-H⋯S hydrogen bonding. In [NH 4][S2CN(CH2CH2OH)2] (1), a 3-D network is found mediated by cooperative O-H⋯S, N-H⋯O and N-H⋯S hydrogen bonding. Reducing the hydrogen bonding functionality by replacing the ammonium cation in (1) by the 4-aza-1-azoniabicyclo(2.2.2)octanium cation to give [DABCO-H][S2CN(CH2CH2OH) 2] (2), results in a 2-D array. Further reduction of the hydrogen bonding functionality, this time by substituting a CH2CH 2OH with an alkyl group to give [DABCO-H][S2CN(CH 2CH2OH)CH3] (3) and [DABCO-H][S 2CN(CH2CH2OH)CH2CH3] (4) allows for the formation of 1-D supramolecular chains. The introduction of alkali metal cations rather than protic cations removes the possibility of the hydroxyl-O participating in hydrogen bonding interactions as these now coordinate the alkali metal. In the sodium trihydrate, Na[S 2CN(CH2CH2OH)2]·3H 2O (5), O-H⋯O hydrogen bonds are found along with charge-assisted O-H⋯S contacts so that a 3-D network results. Substituting a CH2CH2OH group with a n-propyl group gives Na[S2CN(CH2CH2OH)CH2CH 2CH3]·2H2O (6) and yields a 2-D array. For the anhydrous K[S2CN(CH2CH2OH)2] (7) and Cs[S2CN(CH2CH2OH)2] (8) salts, the crystal packing is dominated by charge-assisted O-H⋯S hydrogen bonding giving 3-D network structures. The systematic analysis of the crystal packing patterns of these salts reveals the importance of charge-assisted O-H⋯S hydrogen bonding in stabilising these crystal structures.

Original languageEnglish
Pages (from-to)1626-1637
Number of pages12
JournalCrystEngComm
Volume10
Issue number11
DOIs
Publication statusPublished - 4 Nov 2008
Externally publishedYes

Fingerprint

Anions
Cations
Hydrogen bonds
Negative ions
Agglomeration
Positive ions
anions
cations
hydrogen
interactions
Alkali Metals
Salts
salts
Alkali metals
alkali metals
Hydroxyl Radical
Crystals
crystals
Ammonium Compounds
sodium

Cite this

Howie, R. Alan ; De Lima, Geraldo M. ; Menezes, Daniele C. ; Wardell, James L. ; Wardell, Solange M.S.V. ; Young, David J. ; Tiekink, Edward R.T. / The influence of cation upon the supramolecular aggregation patterns of dithiocarbamate anions functionalised with hydrogen bonding capacity - The prevalence of charge-assisted O-H⋯S interactions. In: CrystEngComm. 2008 ; Vol. 10, No. 11. pp. 1626-1637.
@article{aad472bafa2e4e9382f01773939c5534,
title = "The influence of cation upon the supramolecular aggregation patterns of dithiocarbamate anions functionalised with hydrogen bonding capacity - The prevalence of charge-assisted O-H⋯S interactions",
abstract = "A range of supramolecular architectures is found in the title dithiocarbamate salts, each with hydrogen bonding functionality in the form of aτ least one hydroxyl group. A common feature in the crystal packing is the prevalence of charge-assisted O-H⋯S hydrogen bonding. In [NH 4][S2CN(CH2CH2OH)2] (1), a 3-D network is found mediated by cooperative O-H⋯S, N-H⋯O and N-H⋯S hydrogen bonding. Reducing the hydrogen bonding functionality by replacing the ammonium cation in (1) by the 4-aza-1-azoniabicyclo(2.2.2)octanium cation to give [DABCO-H][S2CN(CH2CH2OH) 2] (2), results in a 2-D array. Further reduction of the hydrogen bonding functionality, this time by substituting a CH2CH 2OH with an alkyl group to give [DABCO-H][S2CN(CH 2CH2OH)CH3] (3) and [DABCO-H][S 2CN(CH2CH2OH)CH2CH3] (4) allows for the formation of 1-D supramolecular chains. The introduction of alkali metal cations rather than protic cations removes the possibility of the hydroxyl-O participating in hydrogen bonding interactions as these now coordinate the alkali metal. In the sodium trihydrate, Na[S 2CN(CH2CH2OH)2]·3H 2O (5), O-H⋯O hydrogen bonds are found along with charge-assisted O-H⋯S contacts so that a 3-D network results. Substituting a CH2CH2OH group with a n-propyl group gives Na[S2CN(CH2CH2OH)CH2CH 2CH3]·2H2O (6) and yields a 2-D array. For the anhydrous K[S2CN(CH2CH2OH)2] (7) and Cs[S2CN(CH2CH2OH)2] (8) salts, the crystal packing is dominated by charge-assisted O-H⋯S hydrogen bonding giving 3-D network structures. The systematic analysis of the crystal packing patterns of these salts reveals the importance of charge-assisted O-H⋯S hydrogen bonding in stabilising these crystal structures.",
author = "Howie, {R. Alan} and {De Lima}, {Geraldo M.} and Menezes, {Daniele C.} and Wardell, {James L.} and Wardell, {Solange M.S.V.} and Young, {David J.} and Tiekink, {Edward R.T.}",
year = "2008",
month = "11",
day = "4",
doi = "10.1039/b809730e",
language = "English",
volume = "10",
pages = "1626--1637",
journal = "CrystEngComm",
issn = "1466-8033",
publisher = "Royal Society of Chemistry (RSC)",
number = "11",

}

The influence of cation upon the supramolecular aggregation patterns of dithiocarbamate anions functionalised with hydrogen bonding capacity - The prevalence of charge-assisted O-H⋯S interactions. / Howie, R. Alan; De Lima, Geraldo M.; Menezes, Daniele C.; Wardell, James L.; Wardell, Solange M.S.V.; Young, David J.; Tiekink, Edward R.T.

In: CrystEngComm, Vol. 10, No. 11, 04.11.2008, p. 1626-1637.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - The influence of cation upon the supramolecular aggregation patterns of dithiocarbamate anions functionalised with hydrogen bonding capacity - The prevalence of charge-assisted O-H⋯S interactions

AU - Howie, R. Alan

AU - De Lima, Geraldo M.

AU - Menezes, Daniele C.

AU - Wardell, James L.

AU - Wardell, Solange M.S.V.

AU - Young, David J.

AU - Tiekink, Edward R.T.

PY - 2008/11/4

Y1 - 2008/11/4

N2 - A range of supramolecular architectures is found in the title dithiocarbamate salts, each with hydrogen bonding functionality in the form of aτ least one hydroxyl group. A common feature in the crystal packing is the prevalence of charge-assisted O-H⋯S hydrogen bonding. In [NH 4][S2CN(CH2CH2OH)2] (1), a 3-D network is found mediated by cooperative O-H⋯S, N-H⋯O and N-H⋯S hydrogen bonding. Reducing the hydrogen bonding functionality by replacing the ammonium cation in (1) by the 4-aza-1-azoniabicyclo(2.2.2)octanium cation to give [DABCO-H][S2CN(CH2CH2OH) 2] (2), results in a 2-D array. Further reduction of the hydrogen bonding functionality, this time by substituting a CH2CH 2OH with an alkyl group to give [DABCO-H][S2CN(CH 2CH2OH)CH3] (3) and [DABCO-H][S 2CN(CH2CH2OH)CH2CH3] (4) allows for the formation of 1-D supramolecular chains. The introduction of alkali metal cations rather than protic cations removes the possibility of the hydroxyl-O participating in hydrogen bonding interactions as these now coordinate the alkali metal. In the sodium trihydrate, Na[S 2CN(CH2CH2OH)2]·3H 2O (5), O-H⋯O hydrogen bonds are found along with charge-assisted O-H⋯S contacts so that a 3-D network results. Substituting a CH2CH2OH group with a n-propyl group gives Na[S2CN(CH2CH2OH)CH2CH 2CH3]·2H2O (6) and yields a 2-D array. For the anhydrous K[S2CN(CH2CH2OH)2] (7) and Cs[S2CN(CH2CH2OH)2] (8) salts, the crystal packing is dominated by charge-assisted O-H⋯S hydrogen bonding giving 3-D network structures. The systematic analysis of the crystal packing patterns of these salts reveals the importance of charge-assisted O-H⋯S hydrogen bonding in stabilising these crystal structures.

AB - A range of supramolecular architectures is found in the title dithiocarbamate salts, each with hydrogen bonding functionality in the form of aτ least one hydroxyl group. A common feature in the crystal packing is the prevalence of charge-assisted O-H⋯S hydrogen bonding. In [NH 4][S2CN(CH2CH2OH)2] (1), a 3-D network is found mediated by cooperative O-H⋯S, N-H⋯O and N-H⋯S hydrogen bonding. Reducing the hydrogen bonding functionality by replacing the ammonium cation in (1) by the 4-aza-1-azoniabicyclo(2.2.2)octanium cation to give [DABCO-H][S2CN(CH2CH2OH) 2] (2), results in a 2-D array. Further reduction of the hydrogen bonding functionality, this time by substituting a CH2CH 2OH with an alkyl group to give [DABCO-H][S2CN(CH 2CH2OH)CH3] (3) and [DABCO-H][S 2CN(CH2CH2OH)CH2CH3] (4) allows for the formation of 1-D supramolecular chains. The introduction of alkali metal cations rather than protic cations removes the possibility of the hydroxyl-O participating in hydrogen bonding interactions as these now coordinate the alkali metal. In the sodium trihydrate, Na[S 2CN(CH2CH2OH)2]·3H 2O (5), O-H⋯O hydrogen bonds are found along with charge-assisted O-H⋯S contacts so that a 3-D network results. Substituting a CH2CH2OH group with a n-propyl group gives Na[S2CN(CH2CH2OH)CH2CH 2CH3]·2H2O (6) and yields a 2-D array. For the anhydrous K[S2CN(CH2CH2OH)2] (7) and Cs[S2CN(CH2CH2OH)2] (8) salts, the crystal packing is dominated by charge-assisted O-H⋯S hydrogen bonding giving 3-D network structures. The systematic analysis of the crystal packing patterns of these salts reveals the importance of charge-assisted O-H⋯S hydrogen bonding in stabilising these crystal structures.

UR - http://www.scopus.com/inward/record.url?scp=54949120254&partnerID=8YFLogxK

U2 - 10.1039/b809730e

DO - 10.1039/b809730e

M3 - Article

VL - 10

SP - 1626

EP - 1637

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 11

ER -