Experimental charge density in an oxidized trinuclear iron complex using 15 K synchrotron and 100 K conventional single-crystal X-ray diffraction

2009 ◽  
pp. 664-671 ◽  
Author(s):  
Jacob Overgaard ◽  
Finn K. Larsen ◽  
Grigore A. Timco ◽  
Bo B. Iversen
2017 ◽  
Vol 74 (1) ◽  
pp. 108-112 ◽  
Author(s):  
Urszula Anna Budniak ◽  
Paulina Maria Dominiak

Isoguanine, an analogue of guanine, is of intrinsic interest as a noncanonical nucleobase. The crystal structure of isoguaninium chloride (systematic name: 6-amino-2-oxo-1H,7H-purin-3-ium chloride), C5H6N5O+·Cl−, has been determined by single-crystal X-ray diffraction. Structure analysis was supported by electrostatic interaction energy (E es) calculations based on charge density reconstructed with the UBDB databank. In the structure, two kinds of molecular tapes are observed, one parallel to (010) and the other parallel to (50\overline{4}). The tapes are formed by dimers of isoguaninium cations interacting with chloride anions. E es analysis indicates that cations in one kind of tape are oriented so as to minimize repulsive electrostatic interactions.


2007 ◽  
Vol 62 (9) ◽  
pp. 1117-1122 ◽  
Author(s):  
Ji-Xiang Dai ◽  
Fang-Hui Wu ◽  
Alexander Rothenberger ◽  
Qian-Feng Zhang

Treatment of the μ3-oxo-centered mixed-valent trinuclear iron complex [Fe3(μ3-O)(μ-OAc)6- (H2O)3] (1) in methanol solution with one, two, or three equivalents of 1-methyl-imidazole (C4H6N2) afforded the substitution products [Fe3(μ3-O)(μ-OAc)6(H2O)2(C4H6N2)] (2), [Fe3(μ3-O)(μ-OAc)6- (H2O)(C4H6N2)2] (3), and [Fe3(μ3-O)(μ-OAc)6(C4H6N2)3] (4), respectively. Complexes 2 - 4 were characterized by spectroscopic and elemental analyses, and the crystal structures of complexes 3 · 1.5MeOH· 2H2O and 4 have been determined by single-crystal X-ray diffraction. The results indicate that in 2 - 4 the trinuclear core unit [Fe3(μ3-O)(μ-OAc)6] of 1 is preserved.


2010 ◽  
Vol 66 (5) ◽  
pp. 559-567 ◽  
Author(s):  
Rafał Janicki ◽  
Przemysław Starynowicz

The experimental charge density distribution in aminomethylphosphonic acid has been determined from X-ray diffraction and its topological features have been analyzed. The results have shown that the P—O bonds are highly polarized, moreover the P—OH bond is weaker than the bonds to unprotonated O atoms. These facts have been confirmed by theoretical density functional theory (DFT) calculations, which have shown that the single, strongly polarized bonds within the phosphonate group are modified by hyperconjugation effects.


2018 ◽  
Vol 233 (9-10) ◽  
pp. 723-731
Author(s):  
Christian Joseph Schürmann ◽  
Regine Herbst-Irmer ◽  
Thorsten Lennart Teuteberg ◽  
Daniel Kratzert ◽  
Gerhard Erker ◽  
...  

Abstract The charge density distribution of the intramolecular frustrated Lewis pair (FLP) Mes2PCH2CH2B(C6F5)2 (1), the phosphinimine HNPMes2CH2CH2B(C6F5)2 (2), as well as a FLP homologue with nitrogen NEt2CHPhCH2B(C6F5)2 (3) were investigated with Bader’s quantum theory of atoms in molecules (QTAIM). The charge densities were derived from both experimental high-resolution X-ray diffraction data (2, 3) and theoretical calculations (1, 3). The QTAIM analysis for the FLPs 1 and 3 showed the prominent B-pnictogen interaction to be weak dative bonds without significant charge-transfer. This holds also true for the B–N–bond of 2. The nitrogen atom is negatively charged, due to a charge transfer from phosphorous and shows features of a sp2-hybridization. The bond is therefore best described as a non-hypervalent Pδ+–Nδ− moiety.


2014 ◽  
Vol 70 (a1) ◽  
pp. C1345-C1345
Author(s):  
Verena Breuers ◽  
Christian Lehmann ◽  
Walter Frank

The first λ3,λ5-tetraphosphete contains a 4π-electron four-membered ring as the central structural unit of a dispirocyclic system and can thus be classified as an analogue to diphosphetes and cyclodiphosphazenes. According to its crystal structure the central P4unit exhibits not only P–P bonds which are of equal length (P1–P2 2,139(1) Å, P1–P2A 2,142(1) Å), but also rhombic distortion (P1–P2–P1A 79,4(1)0, P2–P1–P2A 100,6(1)0).[1] Therefore its electronic structure cannot be described as 'Phosphacyclobutadiene' but either as a bis(ylide) or as a system with delocalized double bonds. After various quantum chemical calculations and an extensive examination of its reaction and coordination behavior failed to answer this question, we addressed the problem via a detailed analysis of its charge density distribution. The experimental charge density based on high resolution X-ray diffraction data collected at low temperature is determined by multipole least squares refinement using the program packageXD2006.[2] In a first step, the static deformation density exhibits charge density which is located mainly outside of the P4ring plane at the λ3-phosphorus atoms but simultaneously redistributed into the P–P bond area. In addition to that, a study of its topological properties and an inspection of the Laplacian of the electron density according to Bader's `Quantum Theory of Atoms in Molecules' (QTAIM)[3] further highlight the bonding features. They reveal polar Si–N, Si–C and P–N bonds with a decreasing amount of electrostatic contribution as well as four valence shell charge concentrations (thus sp3hybridization) at each of the phosphorus atoms. Finally supported by theoretical calculations, the results illustrate the unique bonding situation in the P4unit combining a high ylidic character with unusual not exclusively sigma-like P–P bonds.


2010 ◽  
Vol 405 (11) ◽  
pp. S321-S323
Author(s):  
S. Maki ◽  
E. Nishibori ◽  
H. Okabayashi ◽  
R. Sato ◽  
S. Aoyagi ◽  
...  

Author(s):  
J. M. Galbraith ◽  
L. E. Murr ◽  
A. L. Stevens

Uniaxial compression tests and hydrostatic tests at pressures up to 27 kbars have been performed to determine operating slip systems in single crystal and polycrystal1ine beryllium. A recent study has been made of wave propagation in single crystal beryllium by shock loading to selectively activate various slip systems, and this has been followed by a study of wave propagation and spallation in textured, polycrystal1ine beryllium. An alteration in the X-ray diffraction pattern has been noted after shock loading, but this alteration has not yet been correlated with any structural change occurring during shock loading of polycrystal1ine beryllium.This study is being conducted in an effort to characterize the effects of shock loading on textured, polycrystal1ine beryllium. Samples were fabricated from a billet of Kawecki-Berylco hot pressed HP-10 beryllium.


Author(s):  
Süheyla Özbey ◽  
F. B. Kaynak ◽  
M. Toğrul ◽  
N. Demirel ◽  
H. Hoşgören

AbstractA new type of inclusion complex, S(–)-1 phenyl ethyl ammonium percholorate complex of R-(–)-2-ethyl - N - benzyl - 4, 7, 10, 13 - tetraoxa -1- azacyclopentadecane, has been prepared and studied by NMR, IR and single crystal X-ray diffraction techniques. The compound crystallizes in space group


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