Unexpected Hydride: Ce4B2C2H2.42, a Stuffed Variant of the Nd2BC Structure Type

• Published in: Crystal growth & design Vol. 21; no. 9; pp. 5164 - 5171
• Main Authors: Hertz, Mary B, Baumbach, Ryan, Wang, Xiaoping, Latturner, Susan E
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 01.09.2021
• Subjects: Anions; Boron; Crystals; Fluxes; Hydrogen; MATERIALS SCIENCE
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.1c00521

Ce4B2C2H2.42 was grown as large crystals from a cerium/copper eutectic flux. The structure was characterized by single-crystal X-ray and neutron diffraction and was found to be a stuffed variant of Nd2BC with the addition of two interstitial hydrogen positions. The tetrahedral hydrogen position is fully occupied, while the octahedral position has an occupancy of 42(3)%. Initial synthesis was due to hydrogen contamination of the cerium metal but has been successfully repeated using anthracene as a carbon and hydrogen source. Density of states calculations suggest that the incorporation of hydrogen stabilizes the compound with respect to the nonhydrided model. Magnetic susceptibility data show a complex magnetic ordering at 7.7 K that originates from the localized electron on the Ce3+ in the structure. The trivalent state is also supported by X-ray photoelectron spectroscopy measurements. Heat capacity and electrical resistivity data show that the phase transition is broad in temperature, which may be due to structural disorder. The large low temperature value of C/T also indicates possible heavy fermion behavior.