The crystal structures of the Hexakis(pyridine 1-oxide) complexes of copper(II), cobalt(II) and iron(II) perchlorates

1978 ◽  
Vol 31 (4) ◽  
pp. 713 ◽  
Author(s):  
D Taylor
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Teller Distortion ◽  
Space Group ◽  
X Ray ◽  
Perchlorate Ion ◽  
Fourier Techniques ◽  
Jahn Teller ◽  
Jahn Teller Distortion ◽  
Block Diagonal

The crystal structures of the isomorphous complexes [M(pyridine 1-oxide)6] (ClO4)2 M = Cu (1), Co (2) and Fe (3), have been determined from X-ray diffractometer data collected at 293 K. The complexes crystallize in the rhombohedral space group R3 with Z = 1; cell constants for (1): a 9.605(1)Ǻ, α 81.10(1)°; for (2): a 9.619(1)Ǻ, α 81.19(1)°; for (3): a 9.640(1)Ǻ, α 81.06(1)°. The structures were solved by Fourier techniques and refined by block-diagonal least squares to convergence at R, R': (1) 0.037, 0.039 for 1009 reflections; (2) 0.030, 0.038 for 812 reflections; (3) 0.032, 0.041 for 780 reflections with I ≥ 3σ(I). The cations have exact S6 symmetry with the MO6 moiety having almost exact Oh symmetry, which implies for (1) a lack of a static Jahn-Teller distortion. The M-O distances increase (1) 2.076(2), (2) 2.090(1), (3) 2.112(2)Ǻ in the order expected. The geometries of the pyridine 1-oxide ligand and the perchlorate ion are consistent over the three determinations and are normal.

scholarly journals Die Jahn-Teller-Verzerrung in den Kristallstrukturen der Dinatrium-Tetrafluorometallate Na2CuF4 und Na2CrF4 / The Jahn-Teller Distortion in the Crystal Structures of the Disodium-Tetrafluorometallates Na2CuF4 and Na2CrF4

1989 ◽  
Vol 44 (7) ◽  
pp. 715-720 ◽  
Author(s):  
Dietrich Babel ◽  
Michael Otto
Keyword(s):  
Crystal Structures ◽  
Chain Structure ◽  
Teller Distortion ◽  
Space Group ◽  
X Ray ◽  
Edge Sharing Octahedra ◽  
Jahn Teller ◽  
A Chain ◽  
Jahn Teller Distortion ◽  
Ray Methods

The crystal structures of the isotypic monoclinic fluorides Na2CuF4 (a = 326.7(1), b = 937.0(2), c = 561.2(1) pm, β = 92.49(1)°; V = 171.63 x10-30 m3) and Na2CrF4 (a = 334.8(1), b = 954.9(2), c = 566.5(3) pm, β = 92.85(3)°; V = 180.89 × 10-30 m3) have been redetermined by single crystal X-ray methods. The compounds are Jahn-Teller distorted variants of the orthorhombic Sr2PbO4type (space group Pbam) and crystallize with Z = 2 in space group P21/c, a subgroup of Pbam. They form a chain structure of edge-sharing octahedra which are strongly elongated. The following distances were obtained: Cu-F = 190.4/193.8/235,7(2) pm and Cr-F = 199.1/199.7/241.7(4) pm. The geometry is compared to that of the corresponding distorted rutile type difluorides; relations to further compounds are discussed.

Die Kristallstrukturen von Na2CoFeF7 und einer zweiten Modifikation von Na2CuFeF7: Eine weitere Weberit-Variante / The Crystal Structures of Na2CoFeF7 and a Second Modification of Na2CuFeF7: Another Weberite Variant

1992 ◽  
Vol 47 (5) ◽  
pp. 685-692 ◽  
Author(s):  
Matthias Welsch ◽  
Dietrich Babel
Keyword(s):  
Crystal Structures ◽  
The Other ◽  
Intermediate Type ◽  
Teller Distortion ◽  
Space Group ◽  
Jahn Teller ◽  
Structural Relations ◽  
Jahn Teller Distortion

The monoclinic weberites Na2CoFeF7 (a = 1262.2(10), b = 736.0(4), c = 2451.6(20) pm, β = 99.71(5)°) and a second modification of Na2CuFeF7 (a = 1244.4(2), b = 734.3(1), c = 2467.2(5) pm, β = 99.27(3)°), crystallize isotypically in space group C 2/c, Ζ = 16. The structure is an intermediate type between orthorhombic and trigonal weberites, characterized by pairs ofparallel chains of octahedra [MF4F2/2]3- (M = Co, Cu) which run in turn along [110] and [110]. The average distances are Fe-F = 192 pm in the [FeF63- octahedra of both compounds. Considerable splitting of distances occurs in the [CoF6- octahedra (av. Co-F = 201 pm), and by Jahn-Teller distortion even more in those of [CuFJ4- (av. Cu-F = 199 pm). One of the copper surroundings is (pseudo)tetragonally elongated (av. 209/194 pm), the other exhibits an unusual splitting into three long and three short bonds (av. 204/193 pm) in meridional positions. Some structural relations are discussed.

The Preparation and Crystal Structure of Ammonium Bis[citrato(3-)]cuprate(II)

1991 ◽  
Vol 44 (10) ◽  
pp. 1495 ◽  
Author(s):  
RC Bott ◽  
DS Sagatys ◽  
DE Lynch ◽  
G Smith ◽  
CHL Kennard ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Citric Acid ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Teller Distortion ◽  
Space Group ◽  
X Ray ◽  
Jahn Teller ◽  
A Cell ◽  
Jahn Teller Distortion

The copper(II) complex with citric acid (NH4)4 [Cu(C6H5O7)2] has been prepared, and its structure determined by X-ray diffraction, giving a residual R 0.035 for 1208 observed reflections. Crystals are monoclinic, space group P21/c with Z 2 in a cell of dimensions a 8.755(3), b 13.185(4), c 9.364(2)Ǻ, β 113.73(2)°. The complex is a centrosymmetric six-coordinate monomer which is isomorphous with ammonium zinc(II) citrate. However, the Cu-O(hydroxyl) bonds [2.341(3)Ǻ] show Jahn-Teller distortion relative to the Cu-O(carboxyl) bonds [1.969(3) and 1.977(3)Ǻ].

The Interplay of Open-Shell Spin-Coupling and Jahn-Teller Distortion in Benzene Radical Cation Probed by X-ray Spectroscopy

2020 ◽  
Author(s):  
Marta L. Vidal ◽  
Michael Epshtein ◽  
Valeriu Scutelnic ◽  
Zheyue Yang ◽  
Tian Xue ◽  
...  
Keyword(s):  
High Harmonic ◽  
Open Shell ◽  
Spin Coupling ◽  
High Symmetry ◽  
Teller Distortion ◽  
Spectral Window ◽  
X Ray ◽  
Jahn Teller ◽  
X Ray Absorption ◽  
Jahn Teller Distortion

We report a theoretical investigation and elucidation of the x-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization as well as the measurement of<br>the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys.<br>Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence<br>of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation.<br>The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron<br>in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of<br>the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to<br>be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller<br>effect in benzene cation.<br>

Crystal structures and phase transition in (Sr0.8Ce0.2)(Mn1−yCoy)O3(y= 0 and 0.2): the influence of Jahn–Teller distortion

2009 ◽  
Vol 21 (12) ◽  
pp. 124218 ◽  
Author(s):  
Zhaoming Zhang ◽  
Christopher J Howard ◽  
Brendan J Kennedy ◽  
Motohide Matsuda ◽  
Michihiro Miyake
Keyword(s):  
Phase Transition ◽  
Crystal Structures ◽  
Teller Distortion ◽  
Jahn Teller ◽  
Jahn Teller Distortion

An investigation of the electron density of a Jahn–Teller-distorted CrIIcation: the crystal structure and charge density of hexakis(acetonitrile-κN)chromium(II) bis(tetraphenylborate) acetonitrile disolvate

2015 ◽  
Vol 71 (11) ◽  
pp. 936-943 ◽  
Author(s):  
Arumugam Thangavel ◽  
Marika Wieliczko ◽  
Christopher Scarborough ◽  
Birger Dittrich ◽  
John Bacsa
Keyword(s):  
Crystal Structure ◽  
Electron Density ◽  
Topological Analysis ◽  
Electronic Density ◽  
Teller Distortion ◽  
X Ray ◽  
Structure Factors ◽  
Jahn Teller ◽  
Jahn Teller Distortion ◽  
Detailed Picture

In the crystal structure of the title homoleptic CrIIcomplex, [Cr(CH3CN)6](C24H20B)2·CH3CN, the [Cr(CH3CN)6]2+cation is a high-spind4complex with strong static, rather than dynamic, Jahn–Teller distortion. The electron density of the cation was determined by single-crystal X-ray refinements using aspherical structure factors from wavefunction calculations. The detailed picture of the electronic density allowed us to assess the extent and directionality of the Jahn–Teller distortion of the CrIIcation away from idealized octahedral symmetry. The topological analysis of the asphericald-electron density about the CrIIcation showed that there are significant valence charge concentrations along the axial Cr—N axes. Likewise, there were significant valence charge depletions about the CrIIcation along the equatorial Cr—N bonds. These charge concentrations are in accordance with a Jahn–Teller-distorted six-coordinate complex.

Chemistry and Crystal Structures of Some Constituents of Zingiber cassumunar

1979 ◽  
Vol 32 (1) ◽  
pp. 71 ◽  
Author(s):  
T Amatayakul ◽  
J Cannon ◽  
P Dampawan ◽  
T Dechatiwongse ◽  
RF Giles ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Crystal Structures ◽  
Structure Determination ◽  
Aromatic Compounds ◽  
Crystal Structure Determination ◽  
The Novel ◽  
X Ray ◽  
Zingiber Cassumunar ◽  
Block Diagonal

The novel aromatic compounds cis-3-(2',4',5'-trimethoxyphenyl)-4-[(E)-2''',4''',5'''-trimethoxy-styryl]cyclohex-1-ene(1), cis-3-(3',4'-dimethoxyphenyl)-4-[(E)-3''',4'''-dimethoxystyryl]cyclohex-1-ene (2), a substance assigned the tentative structure cis-3-(3',4'-dimethoxyphenyl)-4-[(E)-2''',4''',5'''- trimethoxystyryl]cyclohex-1-ene (3),(E)-4-(3',4'-dimethoxypheny1)but-3-en-1-ol (5), (E)-4-(3',4'-dimethoxypheny1)but-3-en-1-yl acetate (6), and 8-(3',4'-dimethoxyphenyl)-2-methoxynaphtho-1,4- quinone (7) have been isolated from the rhizomes of Zingiber cassurnunav Roxb. (Zingiberaceae). The crystal structures of the cyclohexene derivative (1) and the quinone (7) have been determined from X-ray diffractometer data at 295 K and refined by block diagonal least squares to residuals of 0.046 (2099 'observed' reflections) and 0.093 (1246), respectively. Crystals of compound (1) are triclinic, P1, a 18.027(12), b 10.037(9), c 6.530(5) α, 84.22 (7), β 81.87 (6), γ 85.72 (6)�, Z 2. Crystals of the quinone (7) are monoclinic, P21/a, a 22.89 (1), b 8.022 (5), c 8.458 (5) �, β 91.98 (5)�, Z 4. Although the latter crystal structure determination is imprecise, due largely to the very small size of the crystal available, the solution is unambiguous. A simple two-step synthesis of the quinone (7) has been achieved.

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