Darstellung und Kristallstruktur von Ag2MnO4

Synthese and Crystal Structure of Ag₂MnO₄ Single crystals of Ag₂MnO₄ have been grown from aqueous solution. The crystal structure has been solved and refined using diffractometer data (Pnma, a = 999.8(2); b = 698.9(1); c = 547.4(2) pm). The mean bond-length Mn? O within the tetrahedral anions is 167.9 pm. In spite of similar lattice constants and identical space group, Ag₂MnO₄ is not isostructural to Olivine. The structural differences are discussed.     

Herstellung und Eigenschaften der Verbindungen Sr2(MnO4)OH und Sr2(MnO4)OH·2H2O

Zusammenfassung Es wird die Herstellung der Verbindungen Sr₂(MnO₄)OH und Sr₂(MnO₄)OH·2H₂O beschrieben. Die Gitterkonstanten wurden aus den entsprechenden Pulverdiagrammen berechnet. Die Infrarotabsorptions-und die Reflexionsspektren im Sichtbaren sowie das magnetische und thermische Verhalten wurden untersucht und kurz besprochen.

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Preparation and properties of the compounds Sr₂(MnO₄)OH and Sr₂(MnO₄)OH·2H₂O

Methods for preparation of the anhydrous compound formulated as Sr₂(MnO₄)OH and of its dihydrate are described. Unit cell parameters, which are the same for both substances, have been calculated from X-ray powder diagramms. Infrared absorption and visible reflectance spectra as well as the magnetic and thermal properties are also reported and briefly discussed.

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Mit 4 Abbildung     

Synthese und Aufbau von Ba2MnO3

Synthesis and Structure of Ba₂MnO₃ Single crystals of Ba₂MnO₃ could be prepared by solid state reaction in hydrogen atmosphere. X-ray structure investigations gave a monoclinic unit cell (a = 584; b = 1157.₉; c = 1270.₇ pm; β = 93.7₄°; space group C? Cc). Mn²⁺ forms isolated tetrahedron chains connected by 7-fold coordinated Ba²⁺.     

Die Feinstruktur in den Schwingungs- und elektronischen Absorptionsspektren von [CrO4]2− und [MnO4]−

Finestructure in the Vibrational and Electronic Absorption Spectra of [CrO₄]^2? and [MnO₄]^? The ir and ra spectra of Tl₂[CrO₄] and (C₂H₅)₄N[MnO₄] are measured and assigned. Details of the preresonance- and resonance-Raman effect are discussed. The exact knowledge of the vibrational spectrum enables the understanding of the complicated vibrational finestructure in the electronic absorption spectrum of (C₂H₅)₄N[MnO₄]. For the states of the charge-transfer t₁ → e* bands are found at 15 000, 15 170 cm^?1 for ¹T₁(I), at 17 646, 17 708, 17 809 cm^?1 for ¹T₂(II) and at 17 920, 17 992 and 18 080 cm^?1 for ³T₂(III). The electronic origin for the states of the t₂ → e* chargetransfer is at 24 661 for ¹T₁(IV) and 30 230 cm^?1 for ¹T₂(V). The vibrational coupling is only with the totally symmetric Mn? O-stretching-vibration. Bands at 29 500 cm^?1 and 44 450 cm^?1 are assigned to the ¹T₂-states of the t₁, t₂ → t₂* charge-transfer.     

Über die Verbindung Sr7Mn4O15 und Beziehungen zur Struktur von Sr2MnO4 und α-SrMnO3

On the Compound Sr₇Mn₄O₁₅ and Structure Relations to Sr₂MnO₄ and α-SrMnO₃ The “compound” hitherto described as a α modification of Sr₂MnO₄ is shown to consist of a mixture of SrO and the new monoclinic compound Sr₇Mn₄O₁₅ crystallizing in the space group P 2₁/c, a = 681.78(6), b = 962.24(8), c = 1038.0(1) pm, β = 91.886(7)°, Z = 2. Up to 0.3 mm long black crystals were grown from prereacted Sr₇Mn₄O₁₅, SrO, and SrCl₂ at 1350°C in a sealed platinum tube under argon. Its structure is related to α-SrMnO₃. It contains layers of cornershared double octahedra [O_2/2OMnO₃MnO₂O_1/2]^7? parallel to (100). Above 100 K the magnetism of Sr₇Mn₄O₁₅ follows the Curie Weiss law with Θ ～ -426 K and a moment μ_eff = 3.62 μ_B corresponding Mn⁴⁺.     

Calculation of activation energy of electron-transfer reaction between MnO4 − and MnO 4 2− ions in aqueous medium

Conclusions The activation energy of electron transfer between the manganate and permanganate ions were calculated. The effect of the ionic strength on E _a was discussed. The calculation results were compared with experiment.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 467–468, February, 1977.     

Herstellung keramischer Pulver. IX. Zur Bildung von NiMn2 O4 und ZnMn2O4 durch Zersetzung von [Ni(H2O)6] (MnO4)2 und [Zn(H2O)6] (MnO4)2

Preparation of Ceramic Powders. IX. NiMn₂O₄ and ZnMn₂O₄ Formation by Decomposition of [Ni(H₂O)₆] (MnO₄)₂ and [Zn(H₂O)₆] (MnO₄)₂ Improved preparation of Ba(MnO₄)₂ from BaMnO₄ is reported. Thermal or hydrothermal decomposition of [Ni(H₂O)₆] (MnO₄)₂ yields intermediately an amorphous manganate(IV) which forms crystalline NiMnO₃ and α-Mn₂O₃ in the range T > 400°C. NiMn₂O₄ is formed above 730°C in accordance with the phase diagram. On the other hand, ZnMn₂O₄ is already at 300°C obtained from [Zn(H₂O)₆](MnO₄)₂ at hydrothermal conditions.     

CNDO-molecular orbital calculations of MnO 4 − and MnF 6 4−

CNDO-MO calculations have been made for the tetrahedral MnO ₄ ^– ion and the octahedral MnF ₆ ^4– ion using a transferable parameter scheme for manganese. The results show that the orbital levels for both complex ions are consistent with the ligand field approach.     

Oxygen evolution from BF3/MnO4-

MnO(4)(-) is activated by BF(3) to undergo intramolecular coupling of two oxo ligands to generate O(2). DFT calculations suggest that there should be a spin intercrossing between the singlet and triplet potential energy surfaces on going from the active intermediate [MnO(2)(OBF(3))(2)](-) to the O···O coupling transition state.     

BF3-activated oxidation of alkanes by MnO4 -

The oxidation of alkanes and arylalkanes by KMnO(4) in CH(3)CN is greatly accelerated by the presence of just a few equivalents of BF(3), the reaction occurring readily at room temperature. Carbonyl compounds are the predominant products in the oxidation of secondary C-H bonds. Spectrophotometric and kinetics studies show that BF(3) forms an adduct with KMnO(4) in CH(3)CN, [BF(3).MnO(4)](-), which is the active species responsible for the oxidation of C-H bonds. The rate constant for the oxidation of toluene by [BF(3).MnO(4)](-) is over 7 orders of magnitude faster than by MnO(4)(-) alone. The kinetic isotope effects for the oxidation of cyclohexane, toluene, and ethylbenzene at 25.0 degrees C are as follows: k(C6H12)/k(C6D12) = 5.3 +/- 0.6, k(C7H8)/k(C7D8) = 6.8 +/- 0.5, k(C8H10)/k(C8D10) = 7.1 +/- 0.5. The rate-limiting step for all of these reactions is most likely hydrogen-atom transfer from the substrate to an oxo group of the adduct. A good linear correlation between log(rate constant) and C-H bond energies of the hydrocarbons is found. The accelerating effect of BF(3) on the oxidation of methane by MnO(4)(-) has been studied computationally by the Density Functional Theory (DFT) method. A significant decrease in the reaction barrier results from BF(3) coordination to MnO(4)(-). The BF(3) coordination increases the ability of the Mn metal center to achieve a d(1) Mn(VI) electron configuration in the transition state. Calculations also indicate that the species [2BF(3).MnO(4)](-) is more reactive than [BF(3).MnO(4)](-).     

Synthese und Kristallstrukturen von IMalnBr4 und NaInI4

Inhaltsübersicht. Einkristalle von NaInBr₄ und NaInI₄ erhält man aus Gemengen der binären Komponenten durch langsames Abkühlen der Schmelze. NaInBr₄ gehört zum NaAlCl₄-Typ: Orthorhombisch, P2₁2₁2₁, Z = 4; a = 1108,1(1); b = 1050,7(1); c = 676,1(1) pm. NaInI₄ ist isotyp mit LiAlCl₄: Monoklin, P2₁/c, Z = 4; a = 852,1(2); b = 766,1(2); c = 1558,3(3) pm; β = 92,65(2)°. In beiden Strukturen treten annähernd tetraedrische Baugruppen [InX₄]^– (X = Br, I) auf. Die Koordinationszahl von Na⁺ ist C.N. = 6 (NaInI₄; leicht verzerrt oktaedrisch) bzw. C.N. = 6+1+1 (NaInBr₄; verzerrtes, doppelt bekapptes Prisma). Synthesis and Crystal Structures of NaInBr₄ and NaInI₄ Single crystals of NaInBr₄ and NaInI₄ are obtained from mixtures of the binary components by slow cooling of the melts. NaInBr₄ belongs to the NaAlCl₄ type of structure: Ortho-rhombic, P2₁2₁2₁, Z = 4, a = 1108.1(1), b = 1050.7(1), c = 676.1(1) pm. NaInI₄ is isotypic with LiAlCl₄: Monoclmic, P2₁/c, Z = 4, a = 852.1(2), b = 766.1(2), c = 1558.3(3) pm, β = 92.65(2)°. Almost tetrahedral polyhedra [InX₄]^– (X = Br, I) are characteristic for both structures. The coordination number of Na⁺ is C.N. = 6 (NaInI₄; slightly distorted octahedron) and C.N. = 6+1+1 (NaInBr₄; distorted bicapped trigonal prism), respectively.     

Struktur und Eigenschaften von TlZnPO4 und TlZnAsO4

Structure and Properties of TlZnPO₄ and TlZnAsO₄ TlZnPO₄ and TlZnAsO₄ have polymorphic behavior with two phase transitions (TlZnPO₄: 263°C, 450°C; TlZnAsO₄: 562°C, 752°C) between room temperature and the congruent melting point at 1 090°C for TlZnPO₄ and 930°C for TlZnAsO₄. X-ray diffraction powder patterns have shown, that the compounds are isotypic and crystallize in the monoclinic system with the lattice constants a = 882.8(2), b = 546.2(1), c = 872.9(1) pm, β = 90.61(2)° for TlZnPO₄, a = 895.4(1), b = 562.3(1), c = 892.8(1) pm, β = 91.08(2)° for TlZnAsO₄, Z = 4, space group P2₁. TlZnPO₄ and TlZnAsO₄ belong to the „stuffed derivatives”︁ of the Icmm structure type with a [ZnXO₄]⁻ network of corner linked alternating ZnO₄ and XO₄ tetrahedra (X = P, As) with channels of six-membered rings in the direction of the c axis. These cavities contain the Tl cations. The results of ³¹P MAS-NMR measurement of TlZnPO₄ may be correlated with its structure. The Tl⁺ ionic conductivity at 300°C reaches only values of 4.4 × 10⁻⁸ Ω⁻¹ cm⁻¹ for TlZnPO₄ and 4.5 × 10⁻⁸ Ω⁻¹ cm⁻¹ for TlZnAsO₄.     

Zur Darstellung und Kristallstruktur von RbTlF4 und CsTlF4

Preparation and Crystal Structure of RbTlF₄ and CsTlF₄ RbTlF₄ and CsTlF₄ were synthesized by heating equivalent mixtures of alkaline chlorides or carbonates and Tl₂O₃ under a current of fluorine at 450–500°C. The crystal structure of RbTlF₄ has been determined by single crystal X-ray diffraction methods. The unit cell is orthorhombic with a = 8.252, b = 8.359, c = 6.244 Å (Z = 4); space group: C?Pb2₁a. CsTlF₄ and Tl^ITl^IIIF₄ (“TlF₂”) are isostructural with RbTlF₄. The structure contains layers of 2-dimensionally corner-linked distorted [TlF_4/2F₂]-octahedra, which are connected by rubidium ions.     

Synthese und Kristallstrukturen der Tetrachlorozinkate SrZnCl4 und BaZnCl4

Synthesis and Crystal Structures of the Tetrachlorozincates SrZnCl₄ and BaZnCl₄ The tetrachlorozincates SrZnCl₄ and BaZnCl₄ are obtained from the respective binary chlorides at 550 °C in silica ampoules. SrZnCl₄ (tetragonal, I4₁/a, Z = 4, a = 650.40(7), c = 1437.0(2) pm) crystallizes with the scheelite type of structure, BaZnCl₄ (orthorhombic, Pnna, Z = 4, a = 724.15(6), b = 986.2(2), c = 947.71(8) pm) belongs to the GaCl₂ type of structure. The coordination polyhedra of the cations are the same in both compounds: Sr²⁺ and Ba²⁺ are surrounded by eight Cl^– (trigon‐dodecahedron), Zn²⁺ is tetrahedrally coordinated. For both compounds no phase transitions could be detected between 140 and 620 K.     

Doping effects in single-layered La0.5Sr1.5MnO4 manganite

In this paper we report the results of the synthesis and structural, transport, and magnetic characterization of pure La(0.5)Sr(1.5)MnO(4) and B-site lightly doped samples, i.e. La(0.5)Sr(1.5)Mn(0.95)B(0.05)O(4), where B = Ru, Co, and Ni. The choice was made in order to probe the charge ordering/orbital ordering ground state of the monolayered La(0.5)Sr(1.5)MnO(4) manganite as a consequence of the cation doping. It is shown that even a light doping is successful in suppressing the charge and orbital order found in pure La(0.5)Sr(1.5)MnO(4). No long-range magnetic order has been detected in any of the doped samples but the setup of a spin-glass state with a common freezing temperature ( approximately 22 K). Structural parameters show an anisotropy in the lattice constant variation, with the tetragonal distortion increasing as the cell volume reduces, which may suggest a variation in the orbital character of the e(g) electrons along with the overall cation size.     

Unrestricted CNDO-MO calculations. II. MnO 4 2− and CrO 4 3−

The electronic structures of the tetrahedral molecule ions MnO ₄ ^2– and CrO ₄ ^3– have been investigated within an unrestricted CNDO-MO approximation [Theoret. Chim. Acta (Berl.)20, 317 (1971)]. Calculations assuming the unpaired electron occupies the 3a ₁, 2e, and 4t2 molecular orbitals indicate that the 3a ₁ and2e orbitals have similar orbital energies and that the 4t ₂ orbital is at a higher energy. The experimentally indicated2e orbital for the unpaired electron is obtained with expanded O^1– type atomic orbitals for oxygen and valence metal orbitals of the expanded 3d and plus one ion 4p types. The metal 4s orbitals must be held to the neutral atom type. The optimum valence orbitals above with a slightly contracted 4s type metal orbitals yield the minimum total energy and places the unpaired electron in the 3a ₁ orbital. Since the contracted 4s metal orbital produces results that are not in agreement with experimental data, the method used apparently does not adequately take into account the increased electron-electron repulsions that contracted 4s orbitals produce.     

Zum thermischen Verhalten von Li3MnO4. II [1, 2]. Über α- und β- Li2MnO3

Thermal Behaviour of Li₃MnO₄. II. α- and β-Li₂MnO₃ By thermal decomposition of Li₃MnO₄ we obtained two new forms of Li₂MnO₃: α-Li₂MnO₃ crystallizes due to Guinier-Simon photographs cubic face-centered with a = 4.09₂ Å, β-Li₂MnO₃ hexagonal with a = 4,93, c = 14.24 Å, c/a = 2.89. α-Li₂MnO₃ is paramagnetic with μ = 3,82 B.M. Below the Neel temperature (≈? 50 K) β-Li₂MnO₃ is antiferromagnetic. Effective Coordination Numbers, ECoN, are calculated and discussed.