ORCID Profile
0000-0001-8921-0052
Current Organisation
University of Potsdam
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Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B819157C
Abstract: The X-ray single-crystal structure of methyl 2-aminoisobutyrate hydrochloride (Me-AIB), a non-standard amino acid, is reported at 10, 30, 50, 70 and 100 K. Fourier maps indicate the presence of rotational disorder of the hydrogen atoms of the ester methyl group. To study this effect in detail, high resolution data were collected with synchrotron radiation. The non-spherical molecular electron density was predicted with invariom scattering factors and subtracted from the density obtained from a full multipole refinement. This allows disorder to be distinguished from the molecular electron density at each temperature. The disorder is reduced between 100 K and 30 K, but still detectable even at 10 K. Hence, difference densities can be applied for the purpose of electronic structure validation and have the advantage of an absence of noise over Fourier methods. Ultra-low temperature experiments are foreseen to be useful in reducing such kinds of disorder in ultra-high resolution protein crystallography. Molecular dynamics simulations of Me-AIB at temperatures between 10 and 100 K confirm the temperature dependence of the rotational motion of the methyl group seen experimentally. Modeling disorder in X-ray structure analysis will be an interesting future application of molecular dynamics simulations.
Publisher: American Chemical Society (ACS)
Date: 23-08-2010
DOI: 10.1021/JP100995N
Abstract: The electronic characteristics of the dative N−B bond in three Lewis acid−base adducts, hydrazine borane, hydrazine bisborane, and ammonia trifluoroborane, are analyzed by an approach combining experimental electron density determination with a broad variety of theoretical calculations. Special focus is directed to the weak dihydrogen contacts in hydrazine borane. The Atoms In Molecules partitioning scheme is complemented by additional methods like the Source Function, and the Electron Localizability Indicator. For the multipole-free theoretical models of hydrazine borane and hydrazine bisborane, a weak charge donation from Lewis base to acid of about 0.05 e is found, whereas multipole refinement of theoretical and experimental structure factors resulted in opposite signs for the Lewis acid and base fragments. For ammonia trifluoroborane, the donation from Lewis base to acid is slightly larger (about 0.13 e) in the multipole-free models, and the charges obtained by multipole refinement retain the direction of the charge donation but show quite large variations. The natural population analysis charges predict larger charge donations (0.35 e) from the Lewis bases to the acids for the three title complexes. Although the three compounds exhibit intermolecular interactions of different types and strengths, including classical hydrogen bonds, F···H contacts and the already mentioned dihydrogen bonds, almost no charge transfer is detected between different molecules within the crystal environment. The main electronic effect of the formation of the Lewis acid-base adducts and of the crystallization is an increase in the charge separation within the ammonia/hydrazine fragments, which is supported by all investigated bond and atomic properties. The nature of the dative N-B bond is found to be mainly electrostatic, but with a substantial contribution of covalency. The F-B bonds show similarities and differences from the N-B bonds, which makes a distinction of coordinative (or dative) bonds from polar covalent interactions possible.
Publisher: American Chemical Society (ACS)
Date: 09-02-2011
DOI: 10.1021/JP109576A
Abstract: In an approach combining high resolution X-ray diffraction at low temperatures with density functional calculations, two closo-borates, B12H12(2-) (1) and B10H10(2-) (2), and two arachno-boranes, B10H12L2 (L = amine (3) or acetonitrile (4)), are studied by means of Atoms In Molecules (AIM) theory and Electron Localizability Indicator (ELI-D). The charge transfer via the dative N-B bonds in the arachno-boranes and via dihydrogen contacts in the closo-borates is quantified. The dative N-B bond in 4 is significantly shorter and stronger than that in 3 and in small N-B Lewis acid base adducts from the literature. It is even shorter in the gas phase than in the crystal environment in contrast to the bond shortening in the crystal generally found for N-B Lewis acid-base adducts. Furthermore, the calculated charge transfer in terms of AIM charges is opposite to the expected N → B direction but still weak as found for all other N-B bonds. The intramolecular charge redistributions due to intermolecular interactions are quantified by the AIM and ELI-D analysis of contact ion pairs. The latter method gives a deeper understanding of delocalization effects in the borane cages as well as in the counterions. Since dihydrogen bonds are rarely found in crystal structures, one focus was directed to the topologies of the large number of 58 experimentally found contacts of this type. The analysis reveals that the electron density at the bond critical point, the corresponding Laplace function, and the curvature along the bond path (λ3) show a behavior that clearly discriminates these interactions from classical hydrogen bonds, confirming earlier theoretical findings.
Publisher: International Union of Crystallography (IUCr)
Date: 28-05-2014
DOI: 10.1107/S2053273314010626
Abstract: The temperature dependence of H- U iso in N -acetyl-L-4-hydroxyproline monohydrate is investigated. Imposing a constant temperature-independent multiplier of 1.2 or 1.5 for the riding hydrogen model is found to be inaccurate, and severely underestimates H- U iso below 100 K. Neutron diffraction data at temperatures of 9, 150, 200 and 250 K provide benchmark results for this study. X-ray diffraction data to high resolution, collected at temperatures of 9, 30, 50, 75, 100, 150, 200 and 250 K (synchrotron and home source), reproduce neutron results only when evaluated by aspherical-atom refinement models, since these take into account bonding and lone-pair electron density both invariom and Hirshfeld-atom refinement models enable a more precise determination of the magnitude of H-atom displacements than independent-atom model refinements. Experimental efforts are complemented by computing displacement parameters following the TLS+ONIOM approach. A satisfactory agreement between all approaches is found.
Publisher: Wiley
Date: 16-05-2007
Publisher: American Physical Society (APS)
Date: 18-02-2009
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B802831A
Abstract: In order to contribute to a rational design of optimised protease inhibitors which can covalently block the nucleophilic amino acids of the proteases' active sites, we have chosen three model compounds (aziridine , oxirane and acceptor-substituted olefin ) for the examination of their electron-density distribution. Therefore, high-resolution low temperature (9, 27 and 100 K) X-ray diffraction experiments on single-crystals were carried out with synchrotron and conventional X-radiation. It could be shown by the analysis of the electron density using mainly Bader's Theory of Atoms in Molecules, Volkov's EPMM method for interaction energies, electrostatic potentials and Gatti's Source Function that aziridine is most suitable for drug design in this field. A regioselective nucleophilic attack at carbon atom C1 could be predicted and even hints about the reaction's stereoselectivity could be obtained. Moreover, the comparison between two data sets of aziridine (conventional X-ray source vs. synchrotron radiation) gave an estimate concerning the reproducibility of the quantitative results.
Publisher: American Chemical Society (ACS)
Date: 29-11-2010
DOI: 10.1021/IC1013158
Abstract: In an approach combining high-resolution X-ray diffraction at low temperatures with density functional theory calculations, two closo-borates, B(12)H(12)(2-) (1) and B(10)H(10)(2-) (2), and two arachno-boranes, B(10)H(12)L(2) [L = amine (3) or acetonitrile (4)], were analyzed by means of the atoms-in-molecules (AIM) theory and electron localizability indicator (ELI-D). The two-electron three-center (2e3c) bonds of the borane cages are investigated with the focus on real-space indicators for chemical bonding and electron delocalization. In compound 2, only two of the three expected bond critical points (bcp's) are found. However, a weakly populated ELI-D basin is found for this pair of adjacent B atoms and the delocalization index and the Source contributions are on the same order of magnitude as those for the other pairs. The opposite situation is found in the arachno-boranes, where no ELI-D basins are found for two types of B-B pairs, which, in turn, exhibit a bcp. However, again the delocalization index is on the same order of magnitude for this bonding interaction. The results show that an unambiguous real-space criterion for chemical bonding is not given yet for this class of compounds. The arachno-boranes carry a special B-B bond, which is the edge of the crown-shaped molecule. This bond is very long and extremely curved inward the B-B-B ring. Nevertheless, the corresponding bond ellipticity is quite small and the ELI-D value at the attractor position of the disynaptic valence basin is remarkably larger than those for all other B-B valence basins. Furthermore, the value of the ED is large in relation to the B-B bond length, so that only this bond type does not follow a linear relationship of the ED value at the bcp versus B-B bond distances, which is found for all other B-B bcp's. The results indicate that both 2e2c and 2e3c bonding play a distinct role in borane chemistry.
Publisher: International Union of Crystallography (IUCr)
Date: 30-08-2008
DOI: 10.1107/S0021889808024643
Abstract: A 165 mm Mar CCD detector has been fitted on a large Huber four-circle diffractometer together with a helium cryostat at beamline D3 at Hasylab, DESY in Hamburg. This setup allows fast collection of accurate, short-wavelength, very low temperature X-ray diffraction data for charge-density analysis. As a test ex le, diffraction data have been collected in 10 h on a hydrogen-bonded network system with 15 unique atoms, and the electron density was modelled with the multipole formalism in an X–N procedure using matching-temperature neutron diffraction data collected at Institut Laue Langevin, Grenoble in France.
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2CE26964C
Publisher: Elsevier BV
Date: 07-2010
Publisher: International Union of Crystallography (IUCr)
Date: 15-11-2006
Publisher: Copernicus GmbH
Date: 28-03-2022
DOI: 10.5194/EGUSPHERE-EGU22-9318
Abstract: & & Subduction of carbon-bearing phases throughout Earth& #8217 s history may be an important mechanism of sourcing carbon to the Earth& #8217 s lower mantle. As carbon has very low solubility in mantle silicates, it is primarily present in accessory phases such as carbonates, diamond, or metal carbides. Previous studies indicate that more than half of the carbonate contained in the oceanic crust may survive metamorphism and dehydration in the sub-arc and reach the lower mantle, even though the oxygen fugacity in the deep mantle may not favour their stability [1]. Indeed, the presence of carbonate in ultra-deep diamond inclusions provides evidence for carbonate subduction at least down to the transition zone [2].& & & & The carbonate phases present in the lower mantle depend on their bulk composition, the oxygen fugacity, and on their stability at a given pressure and temperature. Results from high-pressure experiments show that magnesite (MgCO& sub& & /sub& ) can be stable up to deep lower mantle conditions (& #8764 GPa and 2500 K) [3]. Accordingly, magnesite may be considered the most probable carbonate phase present in the deep Earth. Experimental studies on magnesite decarbonation in presence of SiO& sub& & /sub& at lower mantle conditions suggest that magnesite is stable along a cold subducted slab geotherm [4, 5]. However, our understanding of magnesite& #8217 s stability in contact with bridgmanite [(Mg,Fe)SiO& sub& & /sub& ], & the most abundant mineral in the lower mantle, remains incomplete.& & & & Hence, to investigate sub-solidus reactions, melting, decarbonation, and diamond formation in the system MgCO& sub& & /sub& -(Mg,Fe)SiO& sub& & /sub& , we conducted a combination of high-pressure experiments using multi-anvil press and laser-heated diamond anvil cells (LH-DAC) at conditions ranging from 25 to 70 GPa and 1300 to 2100 K.& & & & Multi-anvil experiments at 25 GPa and temperatures below the mantle geotherm (1700 K) show the formation of carbonate-silicate melt associated with stishovite crystallization, indicating incongruent melting of bridgmanite to stishovite, in accordance with the recent finding of Litasov and Shatskiy [4]. LH-DAC data from & em& in situ& /em& X-ray diffraction show crystallization of bridgmanite and stishovite. Diamond crystallization is detected using Raman spectroscopy. A melt phase could not be detected & em& in situ& /em& at high temperatures.& & & & Our results suggest a two-step process that starts with melting at temperatures below the mantle geotherm, followed by crystallization of diamond from the melt produced. & Therefore, we propose that subducted carbonate-bearing silicate rocks will not remain stable in the lower mantle and will instead melt at upper-most lower mantle conditions, fostering diamond formation. Our study also provides additional evidence that diamond production is related to carbonated melt. Consequently, the melting of recycled crust and chemical transfer to the surrounding mantle will hinder the transport of carbon deeper into the lower mantle.& & & & [1] Stagno et al. (2015) Contrib. Mineral. Petrol. 169(2), 16.& br& [2] Brenker et al. (2007) EPSL 260(1-2), 1-9.& br& [3] Binck, et al. (2020) Physical Review Materials, 4(5),1-9.& br& [4] Litasov & Shatskiy (2019) Geochemistry International, 57(9), 1024-1033.& br& [5] Drewitt, et al. (2019).& EPSL,& , 213-222.& &
Publisher: Wiley
Date: 08-11-2007
Abstract: Three high-quality single-crystal X-ray diffraction data sets have been measured under very different conditions on a structurally simple, but magnetically complex, coordination polymer, [Mn(HCOO)(2)(H(2)O)(2)](infinity) (1). The first data set is a conventional 100(2) K Mo(Kalpha) data set, the second is a very high resolution 100(2) K data set measured on a second-generation synchrotron source, while the third data set was measured with a tiny crystal on a high brilliance third-generation synchrotron source at 16(2) K. Furthermore, the magnetic susceptibility (chi) and the heat capacity (C(p)) have been measured from 2 to 300 K on pressed powder. The charge density of 1 was determined from multipole modeling of the experimental structure factors, and overall there is good agreement between the densities obtained separately from the three data sets. When considering the fine density features, the two 100 K data sets agree well with each other, but show small differences to the 16 K data set. Comparison with ab initio theory suggests that the 16 K APS data set provides the most accurate density. Topological analysis of the metal-ligand bonding, experimental 3d orbital populations on the Mn atoms, and Bader atomic charges indicate quite ionic, high-spin metal atoms. This picture is supported by the effective moment estimated from the magnetization measurements (5.840(2) mu(B)), but it is at variance with earlier spin density measurements from polarized neutron diffraction. The magnetic ordering originates from superexchange involving covalent interactions with the ligands, and non-ionic effects are observed in the static deformation density maps as well as in plots of the valence shell charge concentrations. Overall, the present study provides a benchmark charge density that can be used in comparison with future metal formate dihydrate charge densities.
Publisher: International Union of Crystallography (IUCr)
Date: 28-06-2011
DOI: 10.1107/S0021889811021285
Abstract: The decomposition of hexacarbonyltungsten, W(CO) 6 , has been studied. The decomposition was induced by heating W(CO) 6 in an autoclave at 523 K and pressures up to 1.8 MPa, and by laser heating in a diamond anvil cell at pressures between 5 and 18 GPa. The products have been characterized using synchrotron X-ray diffraction, pair distribution function analysis, Raman spectroscopy and scanning electron microscopy. Decomposition in the autoclave at the lower pressures resulted in the formation of a metastable tungsten carbide, W 2 C, with an average particle size of 1–2 nm, and an unidentified nanocrystalline tungsten oxide and nanocrystalline graphite with average particle sizes of 1–2 and 11 nm, respectively. The existence of nanocrystalline graphite was deduced from micro-Raman spectra and the graphite particle size was extracted from the intensities of the Raman modes. The high-pressure decomposition products obtained in the diamond anvil cell are the monoclinic tungsten oxide phase WO 2 and the high-pressure phase W 3 O 8 (I). The approximate average size of the graphite particles formed here was 6–8 nm. The bulk modulus of W(CO) 6 is B 0 ≃ 13 GPa.
No related grants have been discovered for Wolfgang Morgenroth.