An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12
Abstract
A structural study of the complex aminated stereotriads, [(tert-butyldimethylsilyl)oxy]-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (1) and its reduced analogue, [(tert-butyldimethylsilyl)oxy]-4-ethenyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (2), revealed a k12-type second-order phase transition in 1 and phase stability of 2 over the temperature range 100–400 K. The observed phase change in 1 has been linked to the partial ordering of the extensive positional disorder of the high temperature phase upon cooling as revealed by single-crystal X-ray diffraction. The ordering breaks the translational symmetry, introduces differences in the molecular volumes of the packed species, and results in a low-temperature crystal structure with Z'=12. The in situ powder X-ray diffraction studies suggest that the transition occurs between 237 K and 180 K upon cooling, but complete amorphization in the range of 244–274 K during heating complicated the assignment of the transition temperature. Lastly, the observed loss of crystallinity has been linked to the phase transition and implies that the loss of long range order is due to the crystallites undergoing the transformation independently from one another.
- Authors:
-
[1];
[1]
- Univ. of Wisconsin-Madison, Madison, WI (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- Univ. of Wisconsin-Madison, Madison, WI (United States)
- OSTI Identifier:
- 1460085
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Crystal Growth and Design
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 11; Journal ID: ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Vinokur, Anastasiya I., Yakovenko, Andrey, Liu, Lu, Schomaker, Jennifer M., and Guzei, Ilia A. An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12. United States: N. p., 2017.
Web. doi:10.1021/acs.cgd.7b01099.
Vinokur, Anastasiya I., Yakovenko, Andrey, Liu, Lu, Schomaker, Jennifer M., & Guzei, Ilia A. An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12. United States. https://doi.org/10.1021/acs.cgd.7b01099
Vinokur, Anastasiya I., Yakovenko, Andrey, Liu, Lu, Schomaker, Jennifer M., and Guzei, Ilia A. Wed .
"An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12". United States. https://doi.org/10.1021/acs.cgd.7b01099. https://www.osti.gov/servlets/purl/1460085.
@article{osti_1460085,
title = {An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12},
author = {Vinokur, Anastasiya I. and Yakovenko, Andrey and Liu, Lu and Schomaker, Jennifer M. and Guzei, Ilia A.},
abstractNote = {A structural study of the complex aminated stereotriads, [(tert-butyldimethylsilyl)oxy]-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (1) and its reduced analogue, [(tert-butyldimethylsilyl)oxy]-4-ethenyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (2), revealed a k12-type second-order phase transition in 1 and phase stability of 2 over the temperature range 100–400 K. The observed phase change in 1 has been linked to the partial ordering of the extensive positional disorder of the high temperature phase upon cooling as revealed by single-crystal X-ray diffraction. The ordering breaks the translational symmetry, introduces differences in the molecular volumes of the packed species, and results in a low-temperature crystal structure with Z'=12. The in situ powder X-ray diffraction studies suggest that the transition occurs between 237 K and 180 K upon cooling, but complete amorphization in the range of 244–274 K during heating complicated the assignment of the transition temperature. Lastly, the observed loss of crystallinity has been linked to the phase transition and implies that the loss of long range order is due to the crystallites undergoing the transformation independently from one another.},
doi = {10.1021/acs.cgd.7b01099},
journal = {Crystal Growth and Design},
number = 11,
volume = 17,
place = {United States},
year = {Wed Sep 20 00:00:00 EDT 2017},
month = {Wed Sep 20 00:00:00 EDT 2017}
}
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Figures / Tables:
Figure 1: Crystal structures for selected integer Z$^\prime$ values. The number of high-Z structures falls dramatically above Z$^\prime$= 4.
Works referencing / citing this record:
CCDC 1510555: Experimental Crystal Structure Determination: ADUNOF : 5-{[t-butyl(dimethyl)silyl]oxy}-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazepane-2,2-dione
dataset, October 2016
- Vinokur, Anastasiya I.; Yakovenko, Andrey; Liu, Lu
- Cambridge Structural Database (CSD)
CCDC 1510557: Experimental Crystal Structure Determination: ADUNOF01 : 5-((t-butyl(dimethyl)silyl)oxy)-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazepane 2,2-dioxide
dataset, October 2016
- Vinokur, Anastasiya I.; Yakovenko, Andrey; Liu, Lu
- Cambridge Structural Database (CSD)
CCDC 1510558: Experimental Crystal Structure Determination: ADUPAT : 5-((t-butyl(dimethyl)silyl)oxy)-4-(1-fluorohexyl)-4-vinyl-1,2,3-oxathiazepane 2,2-dioxide
dataset, October 2016
- Vinokur, Anastasiya I.; Yakovenko, Andrey; Liu, Lu
- Cambridge Structural Database (CSD)