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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

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]; ORCiD logo [1];  [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Loughborough Univ. (United Kingdom)
  2. 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 = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
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Figures / Tables:

Scheme 1 Scheme 1: Synthesis of 6,12-difluorobenzo[1,2-b:4,5-b’]bis[b]benzothiophene 2.

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