Spektroskopische Untersuchungen zum Jahn-Teller-Effekt des Cu2+-Ions in Verbindungen vom Typ A2CuL6, II / Spectroscopic Investigations with Respect to the Jahn-Teller Effect of Cu(II) in Compounds of the Type A2CuL6, II

1974 ◽  
Vol 29 (9-10) ◽  
pp. 634-641 ◽  
Author(s):  
Claus Friebel
Keyword(s):  
Structure Determination ◽  
Qualitative Agreement ◽  
Spectroscopic Data ◽  
Ligand Field ◽  
Orthorhombic Distortion ◽  
X Ray ◽  
Bond Lengths ◽  
Field Spectroscopy ◽  
Jahn Teller ◽  
Jahn Teller Effect

By means of EPR and ligand field spectroscopy a refinement of the Ba2CuF6 structure within the [CuF4/2F2]2--layers consisting of axially elongated CuF6-octahedra, 2-dimensionally connected by corners in an antiferrodistortive order, is given. In qualitative agreement with a recent structure determination by X-ray analysis the spectroscopic data prove, that the equatorial planes of the coupled CuF6-polyhedra form an angle of 2 γ > 90° (corresponding to a disturbed type of antiferrodistortive order). In contrast to 2 γ= 101° found by the X-ray investigation, the spectroscopic results suggest 2 γ = 119 (± 1)°, the consequence of which is an elongation of the Cu—F bond lengths and a remarkable orthorhombic distortion of the CuF6-octahedra.

Kooperative Jahn-Teller-Wechselwirkungen im HgCu(NCS)4 / Cooperative Jahn-Teller Coupling in HgCu(NCS)4 Crystals

1975 ◽  
Vol 30 (11-12) ◽  
pp. 883-888 ◽  
Author(s):  
Claus Friebel ◽  
Maria J. Gonzalez Garmendia
Keyword(s):  
Structure Determination ◽  
Spectroscopic Data ◽  
Magnetic Dipoles ◽  
Space Group ◽  
X Ray ◽  
Jahn Teller ◽  
Strong Exchange ◽  
Spin Moments ◽  
Group D ◽  
Exchange Narrowing

From EPR measurements on HgCu(NCS)4 crystals (space group D14 2h-Pbcn) a coupling of four differently orientated tetragonally elongated CuN4S2 octahedra with very long axial distances can be deduced. Two at a time of these polyhedra with differently orientated Cu-N axes are ferrodistortively ordered in layers 11(001). The Cu2+ ions of adjacent ferrodistortive layers are coupled in a disturbed type of antiferrodistortive order. The angle 2 γ = 113° between the CuN4 planes of the ferrodistortive layers, resulting from the spectroscopic data, is in approximative agreement with 2 γ = 119° found by X-ray structure determination. A strong exchange narrowing of the EPR line is observed in the (010) plane in an angle of β = ± 22° against the α-axis. From this exchange direction corresponding to the projection of one of the Cu-N axes on the (010) plane, conclusions can be drawn concerning the orientation of the magnetic dipoles connected with the spin moments of the coupled Cu2+ ions.

scholarly journals ESR-Untersuchungen zum Jahn-Teller-Effekt des Cu2+-Ions in oxidischen Perowskiten

1969 ◽  
Vol 24 (10) ◽  
pp. 1518-1525
Author(s):  
C. Friebel ◽  
D. Reinen
Keyword(s):  
Phase Transition ◽  
Tetragonal Phase ◽  
Esr Spectra ◽  
Ligand Field ◽  
X Ray ◽  
Field Spectroscopy ◽  
Jahn Teller ◽  
Low X ◽  
Ligand Field Parameters ◽  
Tetragonal Phase Transition

Abstract The ESR-powder-spectra of the perovskite-mixed-crystals M2II (CuxZn1-xW)O6 [MII=Sr, Ba] and Sr2(CuxZn1-xTe)O6 , which have been investigated by means of conventional X-ray-techniques and ligand-field-spectroscopy 1,2, are described and the results extensively discussed. The conclusions can be summarized as follows: (a) At very low x-values isolated, dynamically Jahn-Teller-distorted CuO6-octahedra are present in the cubic matrices, which can be frozen into tetragonally elongated polyhedra at 4.2 °K; (b) At high x-values the CuO6-entities are statically JT-distorted with the long axes lined up along the c-axis of the macroscopically tetragonal phases; (c) The ESR-spectra around the cubic-tetragonal phase-transition are complex, containing signals of obviously magnetically coupled Cu2+-ions; (d) The g-values "follow" the ligand-field-parameters quantitatively. Comparative data of some other compounds are given.

Spektroskopische Untersuchungen zum Jahn-Teller-Effekt des Cu2+-Ions in Verbindungen vom Typ A2 CuL6, I / Spectroscopic Ivestigations with Respect to the Jahn-Teller-Effect of Cu(II) in Compounds of the Type A2CuL6, I

1974 ◽  
Vol 29 (5-6) ◽  
pp. 295-303 ◽  
Author(s):  
Claus Friebel
Keyword(s):  
Esr Spectra ◽  
Ligand Field ◽  
X Ray ◽  
Octahedral Sites ◽  
Structural Differences ◽  
Structure Determinations ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Ligand Field Spectra ◽  
Atomic Parameters

Structural relations between perovskite-related lattices of the type A2CuL6 and the perovskite compounds A2(12) [BCu](6)L6 (1: 1 order in the octahedral sites, elpasolite type) are demonstrated by two examples, the compounds A,Cu(OH)6 [A = Ba, Sr] and Ba2CuF6. From the ESR spectra a coupling of Jahn-Teller-distorted Cu-ligand-octahedra in these compounds corresponding to a “disturbed” type of antiferrodistortive order can be deduced. This result is in agreement with recent X-ray structure determinations. The ligand field spectra of the hydroxocuprates(II) indicate tetragonally elongated CuO6-octahedra with very long axial distances. From the ESR investigations further conclusions can be drawn concerning structural differences between the Ba- and the Sr-compound [Sr2Cu(OH6)], the atomic parameters of which are still unknown.

Metallkomplexe mit funktionalisierten Schwefelliganden, II . Ruthenium(II)-benzylthiosulfinato Komplexe. Kristallstrukturanalyse von Cp(Ph3P)2Ru[S—S(O)—CH2C6H5]/Metal Complexes of Functionalized Sulfur Containing Ligands, II. Synthesis of Ruthenium (II) B enzyl-thiosulphinato Complexes. X-Ray Structure Determination of Cp(Ph3P)2Ru[S—S(O)—CH2C6H5]

1992 ◽  
Vol 47 (1) ◽  
pp. 39-44 ◽  
Author(s):  
Wolfgang Weigand ◽  
Gabriele Bosl ◽  
Christian Robl
Keyword(s):  
Metal Complexes ◽  
Structure Determination ◽  
Spectroscopic Data ◽  
Chiral Complexes ◽  
X Ray ◽  
Bond Lengths ◽  
Independent Molecules ◽  
Sulfur Containing

(2))CpRu(PPh3)(L)(SH) (L = PPh3 (1), CO compounds react with N-(benzylsulphinyl) phthalim ides to give the chiral complexes CpRu(PPh3)(L)[S-S(O)-CH2-Ph] (4, 5). For 5, a diastereoselectivity of 10:3 is observed. The compounds 4, 5 have been characterized by their spectroscopic data. The X-ray structure d etermination of 4 shows sulphur-sulphur bond lengths of 204,4(4), 205,5(4) and 205,3(4) pm for three independent molecules.

scholarly journals The crystal structure of szenicsite, Cu3MoO4(OH)4

1998 ◽  
Vol 62 (04) ◽  
pp. 461-469 ◽  
Author(s):  
Peter C. Burns
Keyword(s):  
Crystal Structure ◽  
Goodness Of Fit ◽  
Direct Methods ◽  
Ligand Field ◽  
Area Detector ◽  
Vertex Sharing ◽  
Distorted Octahedral ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Least Squares Techniques

Abstract The crystal structure of szenicsite, Cu3MoO4(OH)4, orthorhombic, a = 8.5201(8), b = 12.545(1), c = 6.0794(6) Å, V = 649.8(2) Å3, space group Pnnm, Z = 4, has been solved by direct methods and refined by least-squares techniques to an agreement index (R) of 3.34% and a goodness-of-fit (S) of 1.11 for 686 unique observed [|F| ⩾ 4σF] reflections collected using graphite-monochromated Mo-Kα X-radiation and a CCD area detector. The structure contains three unique Cu2+ positions that are each coordinated by six anions in distorted octahedral arrangements; the distortions of the octahedra are due to the Jahn-Teller effect associated with a d 9 metal in an octahedral ligand-field. The single unique Mo6+ position is tetrahedrally coordinated by four O2− anions. The Cu2+ϕ6 (ϕ: unspecified ligand) octahedra share trans edges to form rutile-like chains, three of which join by the sharing of octahedral edges to form triple chains that are parallel to [001]. The MoO4 tetrahedra are linked to either side of the triple chain of Cu2+ϕ6 octahedra by the sharing of two vertices per tetrahedron, and the resulting chains are cross-linked through tetrahedral-octahedral vertex sharing to form a framework structure. The structure of szenicsite is closely related to that of antlerite, Cu3SO4(OH)4, which contains similar triple chains of edge-sharing Cu2+ϕ6 octahedra.

scholarly journals Über die Reaktion von Wolframhexachlorid mit Se4N2; Kristallstruktur von PPh4[WCl5(NSeCl)] / On the Reaction of Tungsten Hexachloride with Se4N2; Crystal Structure of PPh4[WCl5(NSeCl)]

1991 ◽  
Vol 46 (12) ◽  
pp. 1625-1628 ◽  
Author(s):  
Stefan Vogler ◽  
Werner Massa ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Double Bond ◽  
Structure Determination ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Tetraphenylphosphonium Chloride ◽  
Tungsten Hexachloride

The reaction of tungsten hexachloride with Se4N2 leads to [WCl4(NSeCl)]2, which reacts with pyridine to form [WCl4(NSeCl)Py], and with tetraphenylphosphonium chloride to form PPh4[WCl5(NSeCl)], which was characterized by an X-ray structure determination. Space group P21, Z = 2, 1657 observed unique reflections, R = 0.074, wR = 0.061. Lattice dimensions at —80 C: a = 710.7(1), b = 2217.9(4), c = 953.6(2) pm; β = 111.93(3) . The [WCl5(NSeCl)]- ion possesses an almost linear WNSe group with bond lengths WN = 188 pm, corresponding to a double bond, and NSe = 200 pm.

A Novel Method for Synthesizing Crystalline Copper Carbodiimide, CuNCN. Structure Determination by X-Ray Rietveld Refinement

2005 ◽  
Vol 60 (6) ◽  
pp. 593-596 ◽  
Author(s):  
Xiaohui Liu ◽  
Martial Aime Wankeu ◽  
Heiko Lueken ◽  
Richard Dronskowski
Keyword(s):  
Small Temperature ◽  
Interatomic Distances ◽  
X Ray ◽  
First Order ◽  
Metallic Conductor ◽  
Distorted Octahedral ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Novel Method ◽  
Aqueous Conditions

Well-crystallized copper carbodiimide, CuNCN, was synthesized by the slow oxidation of a copper(I) cyanamide precursor under aqueous conditions. The X-ray powder data evidence the orthorhombic system and space group Cmcm with a = 2.9921(1), b = 6.1782(1), c = 9.4003(2) Å , V = 173.769(5) Å3 and Z = 4. There is a strongly distorted octahedral Cu2+ coordination reflecting a typical first-order Jahn-Teller effect, with interatomic distances of 4×Cu-N = 2.001(2) Å and 2×Cu-N = 2.613(3) Å ; the NCN2− unit adopts the carbodiimide shape with C-N = 1.227(4) Å . Despite the formal d9 electron count of Cu2+, CuNCN exhibits a small temperature-independent paramagnetism and is likely to be a metallic conductor.

Übergangsmetall-Carbin-Komplexe, LXXII [1]. Reaktionen von trans-Bromotetracarbonyl(phenylcarbin)chrom mit Lithiumthiokresolat und Lithiumselenophenolat / Transition Metal Carbyne Complexes, LXXII [1]. Reactions of trans-Bromotetracarbonyl(phenylcarbyne)chromium with Lithium Thiocresolate and Lithium Phenylselenolate

1982 ◽  
Vol 37 (10) ◽  
pp. 1274-1278 ◽  
Author(s):  
Werner Roll ◽  
Ernst Otto Fischer ◽  
Dietmar Neugebauer ◽  
Ulrich Schubert
Keyword(s):  
Hydrochloric Acid ◽  
Transition Metal ◽  
Structure Determination ◽  
Binuclear Complex ◽  
Spectroscopic Data ◽  
Reaction Conditions ◽  
X Ray ◽  
Carbyne Complexes ◽  
Ether Complex

The reaction of trans-bromotetracarbonyl(phenylcarbyne)chromium (1) with lithium phenylselenolate and subsequent protonation with aqueous hydrochloric acid leads to (CO)5Cr[Se2(C6H5)2] (3) and (CO)4Cr(μ-SeC6H5)2Cr(CO)4 (4). From 1 and lithium 4-methylphenylthiolate (CO)5CrC(C6H5)SC6H4CH3 (5) and (CO)5CrS(C2H5)(4-CH3C6H4) (6) are obtained, if triethyloxonium tetrafluoroborate is used instead of hydrochloric acid. The analoguous reaction of 1 with lithium phenylselenolate yields the seleno ether complex (7). Reaction conditions, properties, spectroscopic data and the results of an X-ray structure determination of the binuclear complex (4) are reported.

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