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Synthetic and crystallographic studies of bicyclo[3.3.1]nonane derivatives: from strong to weak hydrogen bonds and the stereochemistry of network formation

Wallentin, Carl-Johan LU ; Orentas, Edvinas; Johnson, Magnus LU ; Bathori, Nikoletta B.; Butkus, Eugenijus; Wendt, Ola LU ; Wärnmark, Kenneth LU and Ohrstrom, Lars (2012) In Crysteengcomm 14(1). p.178-187
Abstract
The syntheses and crystal structures of four unsaturated bicyclo[3.3.1] nonane derivatives containing various functionalities are presented and their intermolecular interactions examined. The impact of unsaturation on crystal structures and intermolecular networks of the six membered rings was found to be significant compared to the saturated analogues. Thus, unsaturated diol rac-1, in striking contrast to its saturated analogue rac-6, does not crystallise with spontaneous resolution. The hydrogen bonds in the starting bicyclononane diene diol rac-1, and the weaker hydrogen bonds in the dienone rac-2, and the bromo and nitrile derivatives, rac-3, rac-4 and (+)-4, respectively, were found significant for the overall structure. The two... (More)
The syntheses and crystal structures of four unsaturated bicyclo[3.3.1] nonane derivatives containing various functionalities are presented and their intermolecular interactions examined. The impact of unsaturation on crystal structures and intermolecular networks of the six membered rings was found to be significant compared to the saturated analogues. Thus, unsaturated diol rac-1, in striking contrast to its saturated analogue rac-6, does not crystallise with spontaneous resolution. The hydrogen bonds in the starting bicyclononane diene diol rac-1, and the weaker hydrogen bonds in the dienone rac-2, and the bromo and nitrile derivatives, rac-3, rac-4 and (+)-4, respectively, were found significant for the overall structure. The two bromine atoms in rac-3 have significant halogen-halogen interactions. In several structures 2D nets can be identified and overall structures can be interpreted as close packing of these layers. The crystal structures were also subject to independent analysis by Hirshfeld surfaces, and this method provided additional insights, especially for the structural role of the unsaturation. The possible relation between chiral networks and conglomerate formation is discussed. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Crysteengcomm
volume
14
issue
1
pages
178 - 187
publisher
Royal Society of Chemistry
external identifiers
  • wos:000300617000028
  • scopus:82955186388
ISSN
1466-8033
DOI
10.1039/c1ce05673e
language
English
LU publication?
yes
id
aa8b883f-60af-4bd7-bbaa-c70047106815 (old id 2409683)
date added to LUP
2012-03-28 12:28:21
date last changed
2017-09-10 04:19:20
@article{aa8b883f-60af-4bd7-bbaa-c70047106815,
  abstract     = {The syntheses and crystal structures of four unsaturated bicyclo[3.3.1] nonane derivatives containing various functionalities are presented and their intermolecular interactions examined. The impact of unsaturation on crystal structures and intermolecular networks of the six membered rings was found to be significant compared to the saturated analogues. Thus, unsaturated diol rac-1, in striking contrast to its saturated analogue rac-6, does not crystallise with spontaneous resolution. The hydrogen bonds in the starting bicyclononane diene diol rac-1, and the weaker hydrogen bonds in the dienone rac-2, and the bromo and nitrile derivatives, rac-3, rac-4 and (+)-4, respectively, were found significant for the overall structure. The two bromine atoms in rac-3 have significant halogen-halogen interactions. In several structures 2D nets can be identified and overall structures can be interpreted as close packing of these layers. The crystal structures were also subject to independent analysis by Hirshfeld surfaces, and this method provided additional insights, especially for the structural role of the unsaturation. The possible relation between chiral networks and conglomerate formation is discussed.},
  author       = {Wallentin, Carl-Johan and Orentas, Edvinas and Johnson, Magnus and Bathori, Nikoletta B. and Butkus, Eugenijus and Wendt, Ola and Wärnmark, Kenneth and Ohrstrom, Lars},
  issn         = {1466-8033},
  language     = {eng},
  number       = {1},
  pages        = {178--187},
  publisher    = {Royal Society of Chemistry},
  series       = {Crysteengcomm},
  title        = {Synthetic and crystallographic studies of bicyclo[3.3.1]nonane derivatives: from strong to weak hydrogen bonds and the stereochemistry of network formation},
  url          = {http://dx.doi.org/10.1039/c1ce05673e},
  volume       = {14},
  year         = {2012},
}