A redetermination of the crystal structure of cupric chloride dihydrate

Brownstein, S.; Han, Nam Fong; Gabe, E. J.; LePage, Y.

doi:10.1524/zkri.1989.189.1-2.13

Cited by 34 publications

(14 citation statements)

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“…Significant paramagnetic shift effects have been observed in 1 H NMR spectra of CuCl 2 •2H 2 O ͑where Cu 2ϩ has a single unpaired electron in a 3d orbital͒ 12,38 and, therefore, we selected the deuterated analog, CuCl 2 •2D 2 O, as a suitable model for the study of 2 H paramagnetic shift interactions. A single crystallographically distinct 2 H site 39,40 results in a single resonance with an isotropic chemical shift of ␦ iso ϭ75.3Ϯ0.5 ppm in the 2 H MAS NMR spectrum ͑not shown͒. The 2 H quadrupolar-echo spectra in Figs.…”

Section: B Copper"ii… Chloride Dihydrate-d 4 "Cucl 2 "2d 2 O…mentioning

confidence: 99%

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Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional H2 (I=1) nuclear magnetic resonance spectroscopy

Antonijevic

Wimperis

2005

The Journal of Chemical Physics

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A novel two-dimensional (2)H (spin I=1) nuclear magnetic resonance technique is introduced for determination of both quadrupole and chemical/paramagnetic shift tensors and their relative orientation. The new method is based upon the well-known quadrupolar-echo experiment and is designed to refocus the quadrupolar interaction at the end of the t(1) evolution period while retaining the modulation introduced by the shift interaction. As a result, a projection of the resulting two-dimensional spectrum onto its F(1) dimension yields a shift anisotropy powder lineshape free from any quadrupolar broadening. The chemical/paramagnetic shifts appear in both F(1) and F(2) dimensions and are thus spread along a +1 frequency gradient; hence, a projection orthogonal to this gradient yields the pure quadrupolar powder lineshape, free from all shift interaction effects. The relative orientation of the quadrupole and shift tensors can be obtained by analysis of the full two-dimensional correlation lineshape. Unlike the well-known double-quantum experiment, the new method is, in principle, equally effective for all values of the quadrupolar splitting, including zero. The properties of the new technique are demonstrated using computer simulation and methods for the extraction of quadrupole and shift tensor parameters are described. The new technique is applied to (diamagnetic) benzoic acid-d(1) (C(6)H(5)CO(2)D) and (paramagnetic) copper(II) chloride dihydrate-d(4) (CuCl(2).2D(2)O).

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Section: B Copper"ii… Chloride Dihydrate-d 4 "Cucl 2 "2d 2 O…mentioning

confidence: 99%

“…The HOH angle for the water molecule is 105°and hence, on this model, the angle ␤ 1 Ј is predicted to be 52.5°. 40 From a comparison of Figs. 11͑c͒ and 11͑d͒ and the experimental spectrum in Fig.…”

Section: B Copper"ii… Chloride Dihydrate-d 4 "Cucl 2 "2d 2 O…mentioning

confidence: 99%

Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional H2 (I=1) nuclear magnetic resonance spectroscopy

Antonijevic

Wimperis

2005

The Journal of Chemical Physics

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“…(NH 4 ) 2 CuBr 4 Ð 2H 2 O (12) 28 in which the copper(II) coordination environment can be described with a CuBr 4 O 2 entity in D 2h symmetry ( Fig. 5(a), Tables 5, 6, S4, S11).…”

Section: Bromocuprates(ii)mentioning

confidence: 99%

Vibrational spectroscopic and force field studies of copper(II) chloride and bromide compounds, and crystal structure of KCuBr₃

Stepakova

Skripkin

Chernykh

et al. 2007

J Raman Spectroscopy

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Vibrational spectroscopic and force field studies have been performed of 15 related copper(II) chloride and copper(II) bromide compounds, including hydrated salts crystallizing in ternary aqueous systems with alkali and ammonium halides. For halocuprates with distorted octahedral coordination characteristic stretching Raman wavenumbers, corresponding to symmetric stretching Cu II -X modes in the equatorial plane, were found in the ranges 247-288 cm −1 for X = Cl, and 173-189 cm −1 for X = Br, while the low-wavenumber stretching modes for the weaker axial Cu-X interactions varied considerably. The tetrahedral coordination for Cs 2 CuCl 4 and Cs 2 CuBr 4 leads to somewhat lower Cu-X symmetric stretching wavenumbers, 295 and 173 cm −1 , respectively. The assignments of the copper-ligand stretching vibrations were performed with the aid of normal coordinate calculations. Correlations between force constants, averaged Cu-X stretching wavenumbers and bond distances have been evaluated considering the following aspects: (1) Jahn-Teller tetragonal distortion (axial elongation) of the octahedral copper(II) coordination environment, (2) differences between terminal and bridging halide ligands (3) effects of coordinated water and the influence of outer-sphere cations. Force constant ratios for terminal and bridging metal-halide bonds reveal characteristic differences between planar and tetrahedrally coordinated M 2 X 6 species. In the hydrated copper(II) halide complexes, the halide ligands are more strongly bound than coordinated water molecules. The crystal structure of KCuBr 3 (K 2 Cu 2 Br 6 ), which was determined to provide structural information for the force field analyses, contains stacks of planar dimeric [Cu 2 Br 6 ] 2− complexes held together by weak axial Cu-Br interactions.

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“…7b). 34 The spins of the Cu 2+ ions are aligned along the Cu-O direction, 35 namely, the Cu  has the smallest energy gap with the HOMO, xz (Fig. 7b).…”

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Prediction of Spin Orientations in Terms of HOMO–LUMO Interactions Using Spin–Orbit Coupling as Perturbation

et al. 2015

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ConspectusFor most chemists and physicists, electron spin is merely a means needed to satisfy the Pauli principle in electronic structure description. However, the absolute orientations of spins in coordinate space can be crucial in understanding the magnetic properties of materials with unpaired electrons. At a low temperature the spins of a magnetic solid may undergo a long-range magnetic ordering, which allows one to determine the directions and magnitudes of spin moments by neutron diffraction refinements. The preferred spin orientation of a magnetic ion can be predicted on the basis of density functional theory (DFT) calculations including electron correlation and spin-orbit coupling (SOC). However, most chemists and physicists are unaware of how the observed and/or calculated spin orientations are related to the local electronic structures of the magnetic ions. This is true even for most crystallographers who determine the directions and magnitudes of spin moments because, for them, they are merely the parameters needed for the diffraction refinements. The objective of this article is to provide a conceptual framework of thinking about and predicting the preferred spin orientation of a magnetic ion by examining the relationship between the spin orientation and the local electronic structure of the ion. In general, a magnetic ion M (i.e., an ion possessing unpaired spins) in a solid or a molecule is surrounded with main-group ligand atoms L to form an MLn polyhedron, where n is typically 2 -6, and the d-states

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A redetermination of the crystal structure of cupric chloride dihydrate

Cited by 34 publications

References 3 publications

Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional H2 (I=1) nuclear magnetic resonance spectroscopy

Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional H2 (I=1) nuclear magnetic resonance spectroscopy

Vibrational spectroscopic and force field studies of copper(II) chloride and bromide compounds, and crystal structure of KCuBr₃

Prediction of Spin Orientations in Terms of HOMO–LUMO Interactions Using Spin–Orbit Coupling as Perturbation

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A redetermination of the crystal structure of cupric chloride dihydrate

Cited by 34 publications

References 3 publications

Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional H2 (I=1) nuclear magnetic resonance spectroscopy

Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional H2 (I=1) nuclear magnetic resonance spectroscopy

Vibrational spectroscopic and force field studies of copper(II) chloride and bromide compounds, and crystal structure of KCuBr3

Prediction of Spin Orientations in Terms of HOMO–LUMO Interactions Using Spin–Orbit Coupling as Perturbation

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Vibrational spectroscopic and force field studies of copper(II) chloride and bromide compounds, and crystal structure of KCuBr₃