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Title: Direct air capture of CO 2 – topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2 )(CO 3 )(H 2 O) 4

Abstract

Chemical bonding and all intermolecular interactions in the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2 )(CO 3 )(H 2 O) 4 , recently employed in the direct air capture of CO 2 via crystallization, have been analyzed within the framework of the quantum theory of atoms in molecules (QTAIM) based on the experimental electron density derived from X-ray diffraction data obtained at 20 K. Accurate hydrogen positions were included based on an analogous neutron diffraction study at 100 K. Topological features of the covalent bonds demonstrate the presence of multiple bonds of various orders within the PyBIGH 2 2+ cation. Strong hydrogen bonds define ribbons comprising carbonate anions and water molecules. These ribbons are linked to stacks of essentially planar dications via hydrogen bonds from the guanidinium moieties and an additional one to the pyridine nitrogen. The linking hydrogen bonds are approximately perpendicular to the anion–water ribbons. The observation of these putative interactions provided motivation to characterize them by topological analysis of the total electron density. Thus, all hydrogen bonds have been characterized by the properties of their (3,−1) bond critical points. Weaker interactions between the PyBIGH 2 2+ cations have similarly been characterized. Integrated atomic charges are also reported.more » A small amount of cocrystallized hydroxide ion (∼2%) was also detected in both the X-ray and neutron data, and included in the multipole model for the electron-density refinement. The small amount of additional H + required for charge balance was not detected in either the X-ray or the neutron data. The results are discussed in the context of the unusually low aqueous solubility of (PyBIGH 2 )(CO 3 )(H 2 O) 4 and its ability to sequester atmospheric CO 2 .« less

Authors:
ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1483904
Alternate Identifier(s):
OSTI ID: 1489578
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
IUCrJ
Additional Journal Information:
Journal Name: IUCrJ Journal Volume: 6 Journal Issue: 1; Journal ID: ISSN 2052-2525
Publisher:
International Union of Crystallography
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon capture; guanidine; X-ray diffraction; neutron diffraction; charge density; topological analysis; crystal engineering; intermolecular interactions; hydrogen bonding; environmental chemistry

Citation Formats

Gianopoulos, Christopher G., Chua, Zhijie, Zhurov, Vladimir V., Seipp, Charles A., Wang, Xiaoping, Custelcean, Radu, and Pinkerton, A. Alan. Direct air capture of CO 2 – topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2 )(CO 3 )(H 2 O) 4. United Kingdom: N. p., 2019. Web. doi:10.1107/S2052252518014616.
Gianopoulos, Christopher G., Chua, Zhijie, Zhurov, Vladimir V., Seipp, Charles A., Wang, Xiaoping, Custelcean, Radu, & Pinkerton, A. Alan. Direct air capture of CO 2 – topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2 )(CO 3 )(H 2 O) 4. United Kingdom. doi:https://doi.org/10.1107/S2052252518014616
Gianopoulos, Christopher G., Chua, Zhijie, Zhurov, Vladimir V., Seipp, Charles A., Wang, Xiaoping, Custelcean, Radu, and Pinkerton, A. Alan. Tue . "Direct air capture of CO 2 – topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2 )(CO 3 )(H 2 O) 4". United Kingdom. doi:https://doi.org/10.1107/S2052252518014616.
@article{osti_1483904,
title = {Direct air capture of CO 2 – topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2 )(CO 3 )(H 2 O) 4},
author = {Gianopoulos, Christopher G. and Chua, Zhijie and Zhurov, Vladimir V. and Seipp, Charles A. and Wang, Xiaoping and Custelcean, Radu and Pinkerton, A. Alan},
abstractNote = {Chemical bonding and all intermolecular interactions in the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2 )(CO 3 )(H 2 O) 4 , recently employed in the direct air capture of CO 2 via crystallization, have been analyzed within the framework of the quantum theory of atoms in molecules (QTAIM) based on the experimental electron density derived from X-ray diffraction data obtained at 20 K. Accurate hydrogen positions were included based on an analogous neutron diffraction study at 100 K. Topological features of the covalent bonds demonstrate the presence of multiple bonds of various orders within the PyBIGH 2 2+ cation. Strong hydrogen bonds define ribbons comprising carbonate anions and water molecules. These ribbons are linked to stacks of essentially planar dications via hydrogen bonds from the guanidinium moieties and an additional one to the pyridine nitrogen. The linking hydrogen bonds are approximately perpendicular to the anion–water ribbons. The observation of these putative interactions provided motivation to characterize them by topological analysis of the total electron density. Thus, all hydrogen bonds have been characterized by the properties of their (3,−1) bond critical points. Weaker interactions between the PyBIGH 2 2+ cations have similarly been characterized. Integrated atomic charges are also reported. A small amount of cocrystallized hydroxide ion (∼2%) was also detected in both the X-ray and neutron data, and included in the multipole model for the electron-density refinement. The small amount of additional H + required for charge balance was not detected in either the X-ray or the neutron data. The results are discussed in the context of the unusually low aqueous solubility of (PyBIGH 2 )(CO 3 )(H 2 O) 4 and its ability to sequester atmospheric CO 2 .},
doi = {10.1107/S2052252518014616},
journal = {IUCrJ},
number = 1,
volume = 6,
place = {United Kingdom},
year = {2019},
month = {1}
}

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DOI: https://doi.org/10.1107/S2052252518014616

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