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 »
- Authors:
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (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. 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. 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 = {Tue Jan 01 00:00:00 EST 2019},
month = {Tue Jan 01 00:00:00 EST 2019}
}
https://doi.org/10.1107/S2052252518014616
Web of Science
Figures / Tables:
Works referenced in this record:
Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures
journal, March 2008
- Macrae, Clare F.; Bruno, Ian J.; Chisholm, James A.
- Journal of Applied Crystallography, Vol. 41, Issue 2
Modern possibilities for calculating some properties of molecules and crystals from the experimental electron density
journal, March 2005
- Stash, A. I.; Tsirelson, V. G.
- Crystallography Reports, Vol. 50, Issue 2
Electron density study of KNiF 3 by the vacuum-camera-imaging plate method
journal, December 1999
- Zhurova, Elizabeth A.; Zhurov, Vladimir V.; Tanaka, Kiyoaki
- Acta Crystallographica Section B Structural Science, Vol. 55, Issue 6
Determination of covalent bond orders and atomic valence indices using topological features of the experimental electron density
journal, January 2007
- Tsirelson, Vladimir G.; Bartashevich, Ekaterina V.; Stash, Adam I.
- Acta Crystallographica Section B Structural Science, Vol. 63, Issue 1
Mantid—Data analysis and visualization package for neutron scattering and SR experiments
journal, November 2014
- Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764
An empirical correction for absorption anisotropy
journal, January 1995
- Blessing, R. H.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 51, Issue 1
Charge Density Analysis of an Organic Ferroelectric. Croconic Acid: an Experimental and Theoretical Study
journal, June 2013
- Zhurov, Vladimir V.; Pinkerton, A. Alan
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 11
Integration of neutron time-of-flight single-crystal Bragg peaks in reciprocal space
journal, May 2014
- Schultz, Arthur J.; Jørgensen, Mads Ry Vogel; Wang, Xiaoping
- Journal of Applied Crystallography, Vol. 47, Issue 3
Learning through a portfolio of carbon capture and storage demonstration projects
journal, January 2016
- Reiner, David M.
- Nature Energy, Vol. 1, Issue 1
Why Capture CO2 from the Atmosphere?
journal, September 2009
- Keith, D. W.
- Science, Vol. 325, Issue 5948
An open-flow helium cryostat for single-crystal X-ray diffraction experiments
journal, October 1998
- Hardie, M. J.; Kirschbaum, K.; Martin, A.
- Journal of Applied Crystallography, Vol. 31, Issue 5
Outlier Treatment in Data Merging
journal, August 1997
- Blessing, R. H.
- Journal of Applied Crystallography, Vol. 30, Issue 4
Advances in protein and small-molecule charge-density refinement methods using MoPro
journal, January 2005
- Jelsch, Christian; Guillot, Benoit; Lagoutte, Angelique
- Journal of Applied Crystallography, Vol. 38, Issue 1
λ/2 contamination in X-ray diffraction data – the impact of heavy atoms
journal, March 2017
- Gianopoulos, Christopher G.; Chua, Zhijie; Zhurov, Vladimir V.
- Journal of Applied Crystallography, Vol. 50, Issue 2
SHADE web server for estimation of hydrogen anisotropic displacement parameters
journal, September 2006
- Madsen, Anders Østergaard
- Journal of Applied Crystallography, Vol. 39, Issue 5
QTAIMC study of the X–H/H⋯O bond order indices (X=O, N, C) in molecular systems
journal, October 2011
- Bartashevich, E. V.; Nikulov, D. K.; Vener, M. V.
- Computational and Theoretical Chemistry, Vol. 973, Issue 1-3
The urgency of the development of CO2 capture from ambient air
journal, July 2012
- Lackner, K. S.; Brennan, S.; Matter, J. M.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 33
Combination of the exact potential and multipole methods (EP/MM) for evaluation of intermolecular electrostatic interaction energies with pseudoatom representation of molecular electron densities
journal, June 2004
- Volkov, Anatoliy; Koritsanszky, Tibor; Coppens, Philip
- Chemical Physics Letters, Vol. 391, Issue 1-3
A Process for Capturing CO2 from the Atmosphere
journal, August 2018
- Keith, David W.; Holmes, Geoffrey; St. Angelo, David
- Joule, Vol. 2, Issue 8
Crystal structure refinement with SHELXL
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
Description of covalent bond orders using the charge density topology
journal, February 2003
- Howard, Siân T.; Lamarche, Olivier
- Journal of Physical Organic Chemistry, Vol. 16, Issue 2
λ/2 Contamination in charge-coupled-device area-detector data
journal, August 1997
- Kirschbaum, K.; Martin, A.; Pinkerton, A. A.
- Journal of Applied Crystallography, Vol. 30, Issue 4
Optimization and evaluation of data quality for charge density studies
journal, March 2008
- Zhurov, Vladimir V.; Zhurova, Elizabeth A.; Pinkerton, A. Alan
- Journal of Applied Crystallography, Vol. 41, Issue 2
Testing aspherical atom refinements on small-molecule data sets
journal, November 1978
- Hansen, N. K.; Coppens, P.
- Acta Crystallographica Section A, Vol. 34, Issue 6
From weak to strong interactions: A comprehensive analysis of the topological and energetic properties of the electron density distribution involving X–H⋯F–Y systems
journal, September 2002
- Espinosa, Enrique; Alkorta, Ibon; Elguero, José
- The Journal of Chemical Physics, Vol. 117, Issue 12
Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities
journal, March 1998
- Espinosa, E.; Molins, E.; Lecomte, C.
- Chemical Physics Letters, Vol. 285, Issue 3-4
WinXPRO : a program for calculating crystal and molecular properties using multipole parameters of the electron density
journal, May 2002
- Stash, Adam; Tsirelson, Vladimir
- Journal of Applied Crystallography, Vol. 35, Issue 3
Data Reduction and Error Analysis for Accurate Single Crystal Diffraction Intensities
journal, January 1987
- Blessing, Robert H.
- Crystallography Reviews, Vol. 1, Issue 1
Experimental electron density overlapping in hydrogen bonds: topology vs. energetics
journal, February 1999
- Espinosa, E.; Lecomte, C.; Molins, E.
- Chemical Physics Letters, Vol. 300, Issue 5-6
Cooperative Jahn-Teller induced phase transition of TbVO4 single crystal structure analyses of the tetragonal high temperature phase and the twinned orthorhombic phase below 33 K
journal, January 1999
- Kirschbaum, Kristin; Martin, Anthony; Parrish, Damon A
- Journal of Physics: Condensed Matter, Vol. 11, Issue 23, p. 4483-4490
Direct air capture of CO2 via aqueous-phase absorption and crystalline-phase release using concentrated solar power
journal, May 2018
- Brethomé, Flavien M.; Williams, Neil J.; Seipp, Charles A.
- Nature Energy, Vol. 3, Issue 7
CO 2 Capture from Ambient Air by Crystallization with a Guanidine Sorbent
journal, December 2016
- Seipp, Charles A.; Williams, Neil J.; Kidder, Michelle K.
- Angewandte Chemie International Edition, Vol. 56, Issue 4
CrystalPlan : an experiment-planning tool for crystallography
journal, March 2011
- Zikovsky, Janik; Peterson, Peter F.; Wang, Xiaoping P.
- Journal of Applied Crystallography, Vol. 44, Issue 2
Molecular and crystal properties of ethyl 4,6-dimethyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate from experimental and theoretical electron densities
journal, July 2006
- Tsirelson, V. G.; Stash, A. I.; Potemkin, V. A.
- Acta Crystallographica Section B Structural Science, Vol. 62, Issue 4
High-resolution neutron crystallographic studies of the hydration of the coenzyme cob(II)alamin
journal, May 2011
- Jogl, Gerwald; Wang, Xiaoping; Mason, Sax A.
- Acta Crystallographica Section D Biological Crystallography, Vol. 67, Issue 6
[20] Processing of X-ray diffraction data collected in oscillation mode
book, January 1997
- Otwinowski, Zbyszek; Minor, Wladek
- Macromolecular Crystallography Part A, 307-326
Direct Capture of CO2 from Ambient Air
journal, August 2016
- Sanz-Pérez, Eloy S.; Murdock, Christopher R.; Didas, Stephanie A.
- Chemical Reviews, Vol. 116, Issue 19, p. 11840-11876
Single-crystal, time-of-flight, neutron-diffraction structure of hydrogen cis-diacetyltetracarbonylrhenate, [cis-(OC)4Re(CH3CO)2]H: a metallaacetylacetone molecule
journal, February 1984
- Schultz, Arthur J.; Srinivasan, K.; Teller, Raymond G.
- Journal of the American Chemical Society, Vol. 106, Issue 4
A Guide to CO2 Sequestration
journal, June 2003
- Lackner, K. S.
- Science, Vol. 300, Issue 5626, p. 1677-1678