Correction: Towards accurate and precise positions of hydrogen atoms bonded to heavy metal atoms

Woinska, Magdalena; Chodkiewicz, Michał Leszek; Woźniak, Krzysztof

doi:10.1039/d1cc90147h

Cited by 1 publication

(5 citation statements)

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“…The structure of SITKUB is an interesting example of how choosing a different basis set may considerably improve the obtained results. The previously published results 27 were obtained with HAR using the cc-pVTZ-DK basis set, which improved the IAM length of the Rh-H1 bond (1.40(2) Å) to a certain extent (elongation to 1.433(13) Å with HAR) compared to the neutron bond length of 1.531 (11) Å. This means that, whereas the IAM underestimated the Rh− H1 bond length by 0.131 Å, HAR decreased this difference (0.098 Å), which was still far from the neutron result.…”

Section: ■ Tm−h Bond Lengths In Various Structuresmentioning

confidence: 72%

“…The HAR bond lengths were elongated considerably toward the neutron lengths such that both values differed by no more than one HAR standard deviation in three cases (Fe-H1 in QOSZON, Ru-HA in NOBBOX, and Rh-H1 in SITKUB) and less than two standard deviations in one case (Fe-H2 in QOSZON), which is an excellent result. The structures and the results obtained for them have already been presented in our communication discussing the preliminary results for a smaller number of structures Table presents the neutron, IAM, and HAR TM–H and Si–H bond lengths.…”

Section: Tm–h Bond Lengths In Various Structuresmentioning

confidence: 93%

“…The structures and the results obtained for them have already been presented in our communication discussing the preliminary results for a smaller number of structures. 27 Table 6 presents the neutron, IAM, and HAR TM–H and Si–H bond lengths. For QOSZON, the results of HAR with the cc-pVTZ basis set and isotropically refined hydrogen atoms bonded to Fe (H1 and H2) are presented since, in this case, the triple-ζ basis set was superior to the double-ζ one and also H1 and H2 could not be refined anisotropically.…”

Section: Tm–h Bond Lengths In Various Structuresmentioning

confidence: 99%

“…Due to the enumerated obstacles, up until our study, which was presented in a short communication, only six structures of complexes with TM–H bonds have been successfully refined with HAR; ,, complementary neutron data is available for only two of these. Our preliminary study extended the list of successful HARs by four structures with both X-ray and neutron diffraction data available.…”

Section: Introductionmentioning

confidence: 99%

“…Our preliminary study based on five metal organic transition metal hydrides 27 showed that non-relativistic HAR performed for such structures at the B3LYP level of theory and for standard resolution data can bring substantial improvement in terms of TM–H bond lengths provided with sufficient quality diffraction data. Herein, we present an extension of this study in which the previously mentioned five and five additional structures of TM-bound hydrides were studied both with X-ray and neutron diffraction.…”

Section: Introductionmentioning

confidence: 99%

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Hirshfeld Atom Refinement of Metal–Organic Complexes: Treatment of Hydrogen Atoms Bonded to Transition Metals

et al. 2023

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Hydrogen positions in hydrides play a key role in hydrogen storage materials and high-temperature superconductors.Our recently published study of five crystal structures of transitionmetal-bound hydride complexes showed that using aspherical atomic scattering factors for Hirshfeld atom refinement (HAR) resulted in a systematic elongation of metal−hydrogen bonds compared to using spherical scattering factors with the Independent Atom Model (IAM). Even though only standardresolution X-ray data was used, for the highest-quality data, we obtained excellent agreement between the X-ray and the neutronderived bond lengths. We present an extended version of this study including 10 crystal structures of metal−organic complexes containing hydrogen atoms bonded to transition-metal atoms for which both X-ray and neutron data are available. The neutron structures were used as a benchmark, and the X-ray structures were refined by applying Hirshfeld atom refinement using various basis sets and DFT functionals in order to investigate the influence of the technical aspects on the length of metal−hydrogen bonds. The result of including relativistic effects in the Hamiltonian and using a cluster of multipoles simulating interactions with a crystal environment during wave function calculations was examined. The effect of the data quality on the final result was also evaluated. The study confirms that a high quality of experimental data is the key factor allowing us to obtain significant improvement in transition metal (TM)−hydrogen bond lengths from HAR in comparison with the IAM. Individual adjustments and better choices of the basis set can improve hydrogen positions. Average differences between TM− H bond lengths obtained with various DFT functionals upon including relativistic effects or between double-ζ and triple-ζ basis sets were not statistically significant. However, if all bonds formed by H atoms were considered, significant differences caused by different refinement strategies were observed. Finally, we examined the refinement of atomic thermal motions. Anisotropic refinement of hydrogen thermal motions with HAR was feasible only in some cases, and isotropically refined hydrogen thermal motions were in similar agreement with neutron values whether obtained with HAR or with the IAM.

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Section: ■ Tm−h Bond Lengths In Various Structuresmentioning

confidence: 72%

Section: Tm–h Bond Lengths In Various Structuresmentioning

confidence: 93%

Section: Tm–h Bond Lengths In Various Structuresmentioning

confidence: 99%