Hirshfeld surface analysis of crystal packing in aza-aromatic picrate salts

Eric Chan, Simon Grabowsky, J.M. Harrowfield, Ming Shi, Brian Skelton, Alexandre Sobolev, Allan White

Research output: Contribution to journalArticle

14 Citations (Scopus)
128 Downloads (Pure)

Abstract

Single crystal X-ray structure determinations have previously been described for picrate salts of a variety of nitrogen bases. Herein, these have been extended to encompass monoprotonated mono- and oligo-dentate cyclic nitrogen-donor ligand systems derived from pyridine, some via saturation (piperidine and morpholine) and others via lateral extension of the aromatic system (2,2′-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10- phenanthroline, bis(2-pyridyl)amine, 2,2′:6′,2′′- terpyridine, and 8-hydroxyquinoline). Hydrogen-bonding interactions are dominant determinants of the structures, complemented by or in competition with parallel stacking of anion and (aromatic) base planes. Furthermore, nitro⋯nitro, nitro⋯π and phenoxy-O⋯π inter-species contacts play a significant role in the crystal packing. It also appears that cation⋯anion interactions arising from CH(adjacent to NH)⋯O(o-nitro) interactions are more important than the available secondary bifurcating component associated with any NH⋯O(o-nitro) approach, resulting, in many cases, in a bidentate NH⋯HC base approach to an (ON)O⋯O⋯O(NO) triadic array. The nature of the anion-cation interactions and their importance are explored using the Hirshfeld surface method. The precision of the structure determinations establishes the quinonoid form of the picrate to be a widespread contributor. Theoretical calculations on picric acid and the parent pyridinium-picrate ion-pair confirm the energetic favourability of the base-triad approach and the dominance of the quinonoid resonance form. This journal is © the Partner Organisations 2014.
Original languageEnglish
Pages (from-to)4508-4538
Number of pages21
JournalCrystEngComm
Volume16
Issue number21
Early online date16 Apr 2014
DOIs
Publication statusPublished - Jun 2014

Fingerprint

picrates
Surface analysis
Negative ions
Salts
salts
Nitrogen
Crystals
Pyridine
crystals
Anions
Amines
Hydrogen bonds
Positive ions
Ligands
Single crystals
interactions
anions
Oxyquinoline
nitrogen
X rays

Cite this

Chan, Eric ; Grabowsky, Simon ; Harrowfield, J.M. ; Shi, Ming ; Skelton, Brian ; Sobolev, Alexandre ; White, Allan. / Hirshfeld surface analysis of crystal packing in aza-aromatic picrate salts. In: CrystEngComm. 2014 ; Vol. 16, No. 21. pp. 4508-4538.
@article{eadea1b19ac14b89bfe69e8a932ed72f,
title = "Hirshfeld surface analysis of crystal packing in aza-aromatic picrate salts",
abstract = "Single crystal X-ray structure determinations have previously been described for picrate salts of a variety of nitrogen bases. Herein, these have been extended to encompass monoprotonated mono- and oligo-dentate cyclic nitrogen-donor ligand systems derived from pyridine, some via saturation (piperidine and morpholine) and others via lateral extension of the aromatic system (2,2′-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10- phenanthroline, bis(2-pyridyl)amine, 2,2′:6′,2′′- terpyridine, and 8-hydroxyquinoline). Hydrogen-bonding interactions are dominant determinants of the structures, complemented by or in competition with parallel stacking of anion and (aromatic) base planes. Furthermore, nitro⋯nitro, nitro⋯π and phenoxy-O⋯π inter-species contacts play a significant role in the crystal packing. It also appears that cation⋯anion interactions arising from CH(adjacent to NH)⋯O(o-nitro) interactions are more important than the available secondary bifurcating component associated with any NH⋯O(o-nitro) approach, resulting, in many cases, in a bidentate NH⋯HC base approach to an (ON)O⋯O⋯O(NO) triadic array. The nature of the anion-cation interactions and their importance are explored using the Hirshfeld surface method. The precision of the structure determinations establishes the quinonoid form of the picrate to be a widespread contributor. Theoretical calculations on picric acid and the parent pyridinium-picrate ion-pair confirm the energetic favourability of the base-triad approach and the dominance of the quinonoid resonance form. This journal is {\circledC} the Partner Organisations 2014.",
author = "Eric Chan and Simon Grabowsky and J.M. Harrowfield and Ming Shi and Brian Skelton and Alexandre Sobolev and Allan White",
year = "2014",
month = "6",
doi = "10.1039/c4ce00095a",
language = "English",
volume = "16",
pages = "4508--4538",
journal = "CrystEngComm.",
issn = "1466-8033",
publisher = "ROYAL SOC CHEMISTRY",
number = "21",

}

Hirshfeld surface analysis of crystal packing in aza-aromatic picrate salts. / Chan, Eric; Grabowsky, Simon; Harrowfield, J.M.; Shi, Ming; Skelton, Brian; Sobolev, Alexandre; White, Allan.

In: CrystEngComm, Vol. 16, No. 21, 06.2014, p. 4508-4538.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Hirshfeld surface analysis of crystal packing in aza-aromatic picrate salts

AU - Chan, Eric

AU - Grabowsky, Simon

AU - Harrowfield, J.M.

AU - Shi, Ming

AU - Skelton, Brian

AU - Sobolev, Alexandre

AU - White, Allan

PY - 2014/6

Y1 - 2014/6

N2 - Single crystal X-ray structure determinations have previously been described for picrate salts of a variety of nitrogen bases. Herein, these have been extended to encompass monoprotonated mono- and oligo-dentate cyclic nitrogen-donor ligand systems derived from pyridine, some via saturation (piperidine and morpholine) and others via lateral extension of the aromatic system (2,2′-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10- phenanthroline, bis(2-pyridyl)amine, 2,2′:6′,2′′- terpyridine, and 8-hydroxyquinoline). Hydrogen-bonding interactions are dominant determinants of the structures, complemented by or in competition with parallel stacking of anion and (aromatic) base planes. Furthermore, nitro⋯nitro, nitro⋯π and phenoxy-O⋯π inter-species contacts play a significant role in the crystal packing. It also appears that cation⋯anion interactions arising from CH(adjacent to NH)⋯O(o-nitro) interactions are more important than the available secondary bifurcating component associated with any NH⋯O(o-nitro) approach, resulting, in many cases, in a bidentate NH⋯HC base approach to an (ON)O⋯O⋯O(NO) triadic array. The nature of the anion-cation interactions and their importance are explored using the Hirshfeld surface method. The precision of the structure determinations establishes the quinonoid form of the picrate to be a widespread contributor. Theoretical calculations on picric acid and the parent pyridinium-picrate ion-pair confirm the energetic favourability of the base-triad approach and the dominance of the quinonoid resonance form. This journal is © the Partner Organisations 2014.

AB - Single crystal X-ray structure determinations have previously been described for picrate salts of a variety of nitrogen bases. Herein, these have been extended to encompass monoprotonated mono- and oligo-dentate cyclic nitrogen-donor ligand systems derived from pyridine, some via saturation (piperidine and morpholine) and others via lateral extension of the aromatic system (2,2′-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10- phenanthroline, bis(2-pyridyl)amine, 2,2′:6′,2′′- terpyridine, and 8-hydroxyquinoline). Hydrogen-bonding interactions are dominant determinants of the structures, complemented by or in competition with parallel stacking of anion and (aromatic) base planes. Furthermore, nitro⋯nitro, nitro⋯π and phenoxy-O⋯π inter-species contacts play a significant role in the crystal packing. It also appears that cation⋯anion interactions arising from CH(adjacent to NH)⋯O(o-nitro) interactions are more important than the available secondary bifurcating component associated with any NH⋯O(o-nitro) approach, resulting, in many cases, in a bidentate NH⋯HC base approach to an (ON)O⋯O⋯O(NO) triadic array. The nature of the anion-cation interactions and their importance are explored using the Hirshfeld surface method. The precision of the structure determinations establishes the quinonoid form of the picrate to be a widespread contributor. Theoretical calculations on picric acid and the parent pyridinium-picrate ion-pair confirm the energetic favourability of the base-triad approach and the dominance of the quinonoid resonance form. This journal is © the Partner Organisations 2014.

U2 - 10.1039/c4ce00095a

DO - 10.1039/c4ce00095a

M3 - Article

VL - 16

SP - 4508

EP - 4538

JO - CrystEngComm.

JF - CrystEngComm.

SN - 1466-8033

IS - 21

ER -