First Full Structural Characterization of Chloro Formamidinium Salts
- 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
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.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 1439480
- Journal Information:
- Zeitschrift fuer Anorganische und Allgemeine Chemie, Journal Name: Zeitschrift fuer Anorganische und Allgemeine Chemie Journal Issue: 22 Vol. 644; ISSN 0044-2313
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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