Effect of Alkyl Chain Length and Linker Atom on the Crystal Packing in 6,12-Dialkoxy- and 6,12-Dialkylsulfanyl-Benzo[1,2- b :4,5- b']bis[ b ]benzothiophenes
Abstract
The effect of varying the chain length on the solid state conformation and packing of 6,12-dialkoxy- and 6,12-dialkylsulfanyl-benzo[1,2-b:4,5-b']bis[b]benzothiophenes has been studied. The compounds were prepared by SNAr reaction of 6,12-difluorbenzo[1,2-b:4,5-b']bis[b]benzothiophene with alkoxides or alkanethiolates derived from C7-C10 alcohols and alkanethiols. Single crystal X-ray diffraction analysis revealed that all but two compounds crystallize in the triclinic space group P1. Two compounds were obtained as monoclinic crystals with space group P21/c. The alkoxy substituted compounds adopted a molecular conformation with a step from the core and a gauche conformation about the C1'-C2' bond placing the alkyl chains close to parallel with the pentacyclic arene ring system, whereas in the alkylsufanyl derivatives, the alkyl chains were arranged strongly deviated from the plane of the ring, with the sulfur atom antiperiplanar to C3' of the alkyl chain. Finally, NMR measurement of T1 relaxation in CDCl3 showed both the alkoxy and alkylsulfanyl substituents to be freely rotating at ambient temperature in solution, indicating the orientation of the chains in the solid state was due to packing interactions during crystallization.
- Authors:
-
[1];
[1]
- Loughborough Univ. (United Kingdom)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1581750
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Crystal Growth and Design
- Additional Journal Information:
- Journal Volume: 19; Journal Issue: 9; Journal ID: ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Riaz, Shahzad, Edgar, Mark, Elsegood, Mark R. J., Horsburgh, Lynne, Teat, Simon J., Warwick, Thomas G., and Weaver, George W. Effect of Alkyl Chain Length and Linker Atom on the Crystal Packing in 6,12-Dialkoxy- and 6,12-Dialkylsulfanyl-Benzo[1,2- b :4,5- b']bis[ b ]benzothiophenes. United States: N. p., 2019.
Web. doi:10.1021/acs.cgd.9b00644.
Riaz, Shahzad, Edgar, Mark, Elsegood, Mark R. J., Horsburgh, Lynne, Teat, Simon J., Warwick, Thomas G., & Weaver, George W. Effect of Alkyl Chain Length and Linker Atom on the Crystal Packing in 6,12-Dialkoxy- and 6,12-Dialkylsulfanyl-Benzo[1,2- b :4,5- b']bis[ b ]benzothiophenes. United States. https://doi.org/10.1021/acs.cgd.9b00644
Riaz, Shahzad, Edgar, Mark, Elsegood, Mark R. J., Horsburgh, Lynne, Teat, Simon J., Warwick, Thomas G., and Weaver, George W. Mon .
"Effect of Alkyl Chain Length and Linker Atom on the Crystal Packing in 6,12-Dialkoxy- and 6,12-Dialkylsulfanyl-Benzo[1,2- b :4,5- b']bis[ b ]benzothiophenes". United States. https://doi.org/10.1021/acs.cgd.9b00644. https://www.osti.gov/servlets/purl/1581750.
@article{osti_1581750,
title = {Effect of Alkyl Chain Length and Linker Atom on the Crystal Packing in 6,12-Dialkoxy- and 6,12-Dialkylsulfanyl-Benzo[1,2- b :4,5- b']bis[ b ]benzothiophenes},
author = {Riaz, Shahzad and Edgar, Mark and Elsegood, Mark R. J. and Horsburgh, Lynne and Teat, Simon J. and Warwick, Thomas G. and Weaver, George W.},
abstractNote = {The effect of varying the chain length on the solid state conformation and packing of 6,12-dialkoxy- and 6,12-dialkylsulfanyl-benzo[1,2-b:4,5-b']bis[b]benzothiophenes has been studied. The compounds were prepared by SNAr reaction of 6,12-difluorbenzo[1,2-b:4,5-b']bis[b]benzothiophene with alkoxides or alkanethiolates derived from C7-C10 alcohols and alkanethiols. Single crystal X-ray diffraction analysis revealed that all but two compounds crystallize in the triclinic space group P1. Two compounds were obtained as monoclinic crystals with space group P21/c. The alkoxy substituted compounds adopted a molecular conformation with a step from the core and a gauche conformation about the C1'-C2' bond placing the alkyl chains close to parallel with the pentacyclic arene ring system, whereas in the alkylsufanyl derivatives, the alkyl chains were arranged strongly deviated from the plane of the ring, with the sulfur atom antiperiplanar to C3' of the alkyl chain. Finally, NMR measurement of T1 relaxation in CDCl3 showed both the alkoxy and alkylsulfanyl substituents to be freely rotating at ambient temperature in solution, indicating the orientation of the chains in the solid state was due to packing interactions during crystallization.},
doi = {10.1021/acs.cgd.9b00644},
journal = {Crystal Growth and Design},
number = 9,
volume = 19,
place = {United States},
year = {Mon Jul 22 00:00:00 EDT 2019},
month = {Mon Jul 22 00:00:00 EDT 2019}
}
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Figures / Tables:
Scheme 1: Synthesis of 6,12-difluorobenzo[1,2-b:4,5-b’]bis[b]benzothiophene 2.
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