First Full Structural Characterization of Chloro Formamidinium Salts
Abstract
While the synthesis of chloro formamidinium chloride has been known for over one century, no solid‐state structure of a chlorine‐substituted formamidinium compound has been reported up to now. Herein, we describe syntheses, solid‐state structures, and vibrational properties of four chloro formamidinium compounds, namely [ClC(NH 2 ) 2 ]Cl ( 1 ), [ClC(NH 2 ) 2 ](AuCl 4 ) ( 2 ), [ClC(NH 2 ) 2 ] 2 (PdCl 4 ) ( 3 ), and [ClC(NH 2 ) 2 ] 2 (PtCl 6 ) ( 4 ), as determined by single‐crystal X‐ray diffraction (SCXRD). 1 and 3 crystallize in the monoclinic space group P 2 1 / c , 2 in the orthorhombic space group Pbcn , whereas 4 adopts the triclinic space group P 1 . By using a combination of high‐resolution time‐of‐flight neutron powder diffraction, state‐of‐the‐art DFT calculations as well as IR spectroscopy, the prior SCXRD result was fully confirmed and augmented by determining the hydrogen‐bonded molecular networks. First‐principles electronic‐structure calculations corroborate the ionic nature of these salts by showing very flat, molecular‐like bands next to the Fermi level, in addition to indirect bandgaps. This study underlines the upmost importance of complementing diffraction data by ab initio calculations, asmore »
- Authors:
-
- Institute of Inorganic Chemistry RWTH Aachen University 52056 Aachen Germany
- Institute of Inorganic Chemistry RWTH Aachen University 52056 Aachen Germany, Current address: Institute of Condensed Matter and Nanosciences (IMCN) Université catholique de Louvain 1348 Louvain‐la‐Neuve Belgium
- Institute of Inorganic Chemistry RWTH Aachen University 52056 Aachen Germany, Jülich‐Aachen Research Alliance (JARA‐HPC) RWTH Aachen University 52056 Aachen Germany
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1439480
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Zeitschrift fuer Anorganische und Allgemeine Chemie
- Additional Journal Information:
- Journal Name: Zeitschrift fuer Anorganische und Allgemeine Chemie Journal Volume: 644 Journal Issue: 22; Journal ID: ISSN 0044-2313
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Möller, Andreas, George, Janine, and Dronskowski, Richard. First Full Structural Characterization of Chloro Formamidinium Salts. Germany: N. p., 2018.
Web. doi:10.1002/zaac.201800164.
Möller, Andreas, George, Janine, & Dronskowski, Richard. First Full Structural Characterization of Chloro Formamidinium Salts. Germany. https://doi.org/10.1002/zaac.201800164
Möller, Andreas, George, Janine, and Dronskowski, Richard. Wed .
"First Full Structural Characterization of Chloro Formamidinium Salts". Germany. https://doi.org/10.1002/zaac.201800164.
@article{osti_1439480,
title = {First Full Structural Characterization of Chloro Formamidinium Salts},
author = {Möller, Andreas and George, Janine and Dronskowski, Richard},
abstractNote = {While the synthesis of chloro formamidinium chloride has been known for over one century, no solid‐state structure of a chlorine‐substituted formamidinium compound has been reported up to now. Herein, we describe syntheses, solid‐state structures, and vibrational properties of four chloro formamidinium compounds, namely [ClC(NH 2 ) 2 ]Cl ( 1 ), [ClC(NH 2 ) 2 ](AuCl 4 ) ( 2 ), [ClC(NH 2 ) 2 ] 2 (PdCl 4 ) ( 3 ), and [ClC(NH 2 ) 2 ] 2 (PtCl 6 ) ( 4 ), as determined by single‐crystal X‐ray diffraction (SCXRD). 1 and 3 crystallize in the monoclinic space group P 2 1 / c , 2 in the orthorhombic space group Pbcn , whereas 4 adopts the triclinic space group P 1 . By using a combination of high‐resolution time‐of‐flight neutron powder diffraction, state‐of‐the‐art DFT calculations as well as IR spectroscopy, the prior SCXRD result was fully confirmed and augmented by determining the hydrogen‐bonded molecular networks. First‐principles electronic‐structure calculations corroborate the ionic nature of these salts by showing very flat, molecular‐like bands next to the Fermi level, in addition to indirect bandgaps. This study underlines the upmost importance of complementing diffraction data by ab initio calculations, as theory‐derived anisotropic displacement parameters served as fixed numerical entries.},
doi = {10.1002/zaac.201800164},
journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie},
number = 22,
volume = 644,
place = {Germany},
year = {Wed May 30 00:00:00 EDT 2018},
month = {Wed May 30 00:00:00 EDT 2018}
}
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