Crystal structure and bond valence of CaH2 from neutron powder diffraction data

• Published in: Zeitschrift für Kristallographie. Crystalline materials Vol. 225; no. 6; pp. 225 - 229
• Main Authors: Alonso, José Antonio, Retuerto, María, Sanchez-Benitez, Javier, Fernández-Díaz, Maria Teresa
• Format: Journal Article
• Language: English
• Published: De Gruyter Oldenbourg 01.06.2010
• Subjects: Hydrogen production by hydrolysis; Hydrogen storage; Isotope effect; Metal hydride; Neutron powder diffraction
• ISSN: 2194-4946; 2196-7105
• DOI: 10.1524/zkri.2010.1258

The crystal structure of CaH has been studied from neutron powder diffraction (NPD) at 295 K in a non-deuterated sample; a good quality NPD pattern was obtained in spite of the hydrogen incoherent scattering. The structure was refined by the Rietveld method in the Pnma space group (No. 62), = 4, with unit-cell parameters = 5.9600(1), = 3.6006(7) and = 6.8167(1) Å. The two kinds of crystallographically independent H atoms, H1 and H2, are located in tetrahedral and square-pyramidal cavities, respectively, while Ca ions are nine-fold coordinated to hydrogen atoms. The average 〈Ca—H1〉 and 〈Ca—H2〉 bond lengths are 2.279 and 2.544 Å, respectively. Bond valence calculations show that Ca—H1 bonds are under compressive stress, whereas Ca—H2 bonds undergo tensile stress in a structure with a relatively high global instability index. It is also remarkable that the displacement factors for H2 are significantly larger than for H1, suggesting an increased lability for the Ca—H2 bonds. We provide with an analysis of the isotope effect, by comparing the present results on CaH with literature data on CaD ; we indeed observe a higher distortion of the H1 and H2 coordination polyhedra with respect to the deuteride, as observed in other isostructural dihydrides.