Die IR-Spektren von [Cr(O2)2(NH3)3] und K3[Cr(O2)2(CN)3]

The infrared spectra of the title compounds are reported and discussed. The influence of the peroxide groups on the bond properties of the other ligands and some characteristics of the metal—peroxide interactions are analyzed.     

Kristallstruktur von (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2

Crystal Structure of (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ . (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ crystallizes from hydrobromic acid solution of Re₃Br₉ · 2 H₂O and NMe₄Br at 0 – 5°C. The crystal structure (monoclinic; P2₁/m (Nr. 11); a = 967.9(3); b = 1 529.7(4); c = 1 710.9(4) pm; β = 91.66(2)°; Z = 2; R = 0.113; R_w = 0.068) has been determined from four-circle diffractometer data. The structure contains two different cluster units of trivalent rhenium, isolated anionic [Re₃Br₁₁(H₂O)]^2? units and neutral cluster units that are connected through crystal water molecules to chains{[Re₃Br₉(H₂O)₃](H₂O)₂}.     

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 x 3H2O

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 x 3H2O are recorded and analyzed. The observed bands are assigned on the basis of BrO3- and H2O vibrations. Additional bands obtained in the region of v3 and v1 modes in [Cu(H2O)6](BrO3)2 are due to the lifting of degeneracy of v3 modes, since the BrO3- ion occupies a site of lower symmetry. The appearance v1 mode of BrO3- anion at a lower wavenumber (771 cm(-1)) is attributed to the attachment of hydrogen to the BrO3- anion. The presence of three inequivalent bromate groups in the [Al(H2O)6](BrO3)3 x 3H2O structure is confirmed. The lifting of degeneracy of v4 mode indicates that the symmetry of BrO3- anion is lowered in the above crystal from C3v to C1. The appearance of additional bands in the stretching and bonding mode regions of water indicates the presence of hydrogen bonds of different strengths in both the crystals. Temperature dependent Raman spectra of single crystal [Cu(H2O)6](BrO3)2 are recorded in the range 77-523 K for various temperatures. A small structural rearrangement takes place in BrO3- ion in the crystal at 391 K. Hydrogen bounds in the crystal are rearranging themselves leading to the loss of one water molecule at 485 K. This is preceded by the reorientation of BrO3- ions causing a phase transition at 447 K. Changes in intensities and wavenumbers of the bands and the narrowing down of the bands at 77 K are attributed to the settling down of protons into ordered positions in the crystal.     

Syntheses and structural study of trinuclear iron acetates [Fe3O(CH3COO)6(H2O)3]Cl· 6H2O and [Fe3O(CH3COO)6(H2O)3] [FeCl4]· 2CH3COOH

The structure of two trinuclear iron acetates [Fe₃O(CH₃COO)₆(H₂O)₃]Cl· 6H₂O (I) and [Fe₃O(CH₃COO)₆(H_2O)₃][FeCl₄] · 2CH₃COOH (II) was determined by X-ray diffraction analysis. Crystals I and II are ionic and belong to the orthorhombic system with parameters a = 13.704(3), b = 23.332(5), c = 9.167(2) Å, R = 0.0355, space goup P2₁2₁2 for I and a = 10.145(4), b = 15.323(6), c = 22.999(8) Å, R = 0.0752, space group Pbc2₁ for II. The complex cation [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ has a μ₃-O-bridged structure typical for trinuclear iron (III) compounds. As shown by Mössbauer spectroscopy, the iron(III) ions are in the high-spin state. In trinuclear cations, antiferromagnetic exchange interaction takes place between the Fe(III) ions with the exchange parameter J = -26.69 cm^?1 for II (Heisenberg-Dirac-Van Vleck model for D_3h, symmetry).     

Synthesis and Crystal Structure of （H3O）2[Cu3Cl3（H2O）3（NC9H12.5O6）2]

1 INTRODUCTION The polydentate ligand nitrilotripropionic acid, H3ntp[N(CH2CH2COOH)3], has attracted conside- rable research interest in constructing coordination polymers, designing organic-inorganic hybrid mate- rials[1], synthesizing supramolecular compounds[2], etc. due to its high degree of flexibility with three carboxylic acid moieties allowing for a variety of coordination through oxygen atoms[3]. It also pro- vides other versatile properties such as the possibili- ty of inter-…     

Triethylphosphanimin-Komplexe der Acetate von Kupfer(II) und Zink. Kristallstrukturen von [Zn(O2C–CH3)2(HNPEt3)], [Cu5(O2C–CH3)10(HNPEt3)2] und [Cu(O2C–CH3)2(HNPEt3)2]

Triethylphosphanimine Complexes of the Acetates of Copper(II) and Zinc. Crystal Structures of [Zn(O₂C–CH₃)₂(HNPEt₃)], [Cu₅(O₂C–CH₃)₁₀(HNPEt₃)₂], and [Cu(O₂C–CH₃)₂(HNPEt₃)₂] The title compounds originate from the anhydrous acetates of zinc and copper(II) with trimethylsilyl-triethylphosphanimine, Me₃SiNPEt₃, in the presence of water in dichloromethane. They form colourless ( 1 ), bluish-green ( 2 ), and blue ( 3 ), respectively, single crystals, which were characterized by IR spectroscopy and by crystal structure analyses. [Zn(O₂C–CH₃)₂(HNPEt₃)] ( 1 ): Space group P 4 2₁c, Z = 8, lattice dimensions at –83 °C: a = b = 1709.6(2), c = 982.4(1) pm, R = 0.0551. 1 has a polymeric chain structure in which the zinc atoms are μ₂-bridged via the oxygen atoms of one of the two acetato groups, while the second acetato group and the phosphanimine are bonded terminally. [Cu₅(O₂C–CH₃)₁₀(HNPEt₃)₂]( 2 · 4 CH₂Cl₂): Space group P2₁/c, Z = 8, lattice dimensions at –80 °C: a = 1761.18(13), b = 4074.5(2), c = 1733.34(15) pm, β = 91.383(10)°, R = 0.0413. 2 consists of the two structural units [Cu₂(O₂C–CH₃)₄] and [Cu₃(O₂C–CH₃)₆(HNPEt₃)₂], which are connected via two of the acetato groups of the Cu₃-unit along the crystallographic a-axis to form three crystallographically independent polymeric strands. [Cu(O₂C–CH₃)₂(HNPEt₃)₂] ( 3 ): Space group P2₁/n, Z = 2, lattice dimensions at 20 °C: a = 695.49(8), b = 1217.85(10), c = 1380.05(7) pm, β = 96.451(7)°, R = 0.0291. 3 forms monomeric, centrosymmetric molecules with a square planar environment at the Cu atoms.     

[Zn3(PO4)2(H2O)0.8(NH3)1.2]

The structure of the title compound, ammineaquadi‐μ₅‐phosphato‐trizinc(II), [Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2], consists of two parts: (i) PO₄ and ZnO₄ vertex‐sharing tetrahedra arranged in layers parallel to (100) and (ii) ZnO₂(N/O)₂ tetrahedra located between the layers. Elemental analysis establishes the ammine‐to‐water ratio as 3:2. ZnO₂(N/O)₂ tetrahedra are located at special position 4e (site symmetry 2) in C2/c. The two O atoms of ZnO₂(N/O)₂ are bonded to neighbouring P atoms, forming two Zn—O—P linkages and connecting ZnO₂(N/O)₂ tetrahedra with two adjacent bc plane layers. A noteworthy feature of the structure is the presence of NH₃ and H₂O at the same crystallographic position and, consequently, qualitative changes in the pattern of hydrogen bonding and weaker N/O—H...O electrostatic interactions, as compared to two closely related structures.     

K2[Mo2O4(C2O4)2(H2O)2]·3H2O

The crystal and molecular structure of dipotassium di‐μ‐oxo‐bis[aqua(oxalato‐O¹,O²)oxomolybdenum(III)] trihydrate, K₂­[Mo₂O₄(C₂O₄)₂(H₂O)₂]·3H₂O, has been determined from X‐ray diffraction data. In the dimeric anion, which has approximate twofold symmetry, each Mo atom is in a distorted octahedral coordination, being bonded to one terminal oxo‐O atom, two bridging O atoms, two O atoms from the oxalato ligand and one from the water mol­ecule. Bond lengths trans to the multiple‐bonded terminal oxo ligand are larger than those in the cis position, confirming the trans influence as a generally valid rule.     

Synthesis and structure of asymmetric zirconium-substituted silicotungstates, [Zr6O2(OH)4(H2O)3(beta-SiW10O37)3]14- and [Zr4O2(OH)2(H2O)4(beta-SiW10O37)2]10-

The reaction of ZrCl4 with [gamma-SiW10O36]8- in a potassium acetate buffer results in two different products depending on the reactant ratios. The trimeric species [Zr6O2(OH)4(H2O)3(beta-SiW10O37)3]14- (1) consists of three beta23-SiW10O37 units linked by an unprecedented Zr6O2(OH)4(H2O)3 cluster with C1 point group symmetry. The dimeric species [Zr4O2(OH)2(H2O)4(beta-SiW10O37)2]10- (2) consists of beta22- and beta12-SiW10O37 units sandwiching a Zr4O2(OH)2(H2O)4 cluster, which also has C1 symmetry. Polyanion 1 contains more zirconium centers than any other polyoxometalate known to date.     

两个典型氧桥三核铁(Ⅲ)配合物[Fe3O(O2CCH2OC6H5)6(3H2O)]和[Fe3O(TIEO)2(O2CPh)2Cl3]的局域自旋和磁性质的理论探讨

用从头算波函数(UHF或UDFT波函数)代替ZILSH方法中的半经验波函数得到了ABLSH方法，接着用该方法研究了两个典型氧桥三核铁(Ⅲ)配合物[Fe₃O(O₂CCH₂OC₆H₅)₆(3H₂O)]和[Fe₃O(TIEO)₂(O₂CPh)₂Cl₃]的局域自旋和磁性质。通过计算得到的局域自旋结果和前人的具有可比性，同时所得的磁交换耦合常数和实验值很吻合。该方法可作为研究海森堡型磁性系统(HM)的新工具。     

Amphiphilic guest sorption of K2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40] ionic crystal

An ionic crystal K2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40] x 3H2O (1a) is synthesized by the complexation of a Keggin-type polyoxometalate of [alpha-SiW12O40]4- with K+ and a macrocation of [Cr3O(OOCC2H5)6(H2O)3]+. Compound 1a possesses both hydrophilic and hydrophobic channels in the crystal lattice. The 3 mol mol(-1) of the water of crystallization in 1a resides in the hydrophilic channel. The water of crystallization is removed by the evacuation at 303 K to form the guest-free phase 1b with small changes in the lattice lengths (+/-0.2 A). The water sorption profile is reproduced by the single rate constant. Therefore, the water sorbed probably resides in the hydrophilic channel. Compound 1b sorbs various kinds of polar organic molecules, and the amounts of < or = C3 alcohols are comparable to or larger than that of water, while chlorocarbons with no hydrogen-bonding ability and nonpolar molecules are excluded. Thus, 1b showed the amphiphilic sorption property. The states of the polar organic molecules sorbed in 1b have been quantitatively investigated using ethanol as a probe molecule. The IR, NMR, and single-crystal X-ray diffraction studies combined with the sorption kinetics reveal that ethanol molecules are mainly sorbed into the hydrophilic channel at P/P0 < or = 0.5, while the sorption into the hydrophobic channel is dominant at P/P0 > or = 0.6. Thus, it is demonstrated that ethanol molecules enter both hydrophilic and hydrophobic channels of 1b.     

CRYSTAL STRUCTURE OF [Sm(CCl_3COO)_3(H_2O)_2]·2H_2O

<正> Biaqua-trichloroacetate-samarium dihydrate, [Sm(CCl3COO)3(H2O)2]-2H2O, Mr=707.54, orthorhombic, space group Pnne, with a = 19.158(5), b = 22.176(4), c= 9.798(4)A, Z= 8, V= 4162.7A3.F{000)= 2696,λ(MoKα)=0.71069A, Dx = 2.258 g/cm3, final R=0.061. The title compound has non-molecular structural character, and its structural units Sm(μ-CCl3COO)s/2-(H2O>2 constitute 2-dinensional infinite chains of Sm(μ-CCl3COO)4Sm(μ-CCl3-COO)2Sm.The Sa(Ⅲ) atom in each unit is bound to two O atoms from aqua-molecules and six 0 atoms from six bridging CCl3COO groups (four of which are shared with the SB atom of another unit, two shared with the Sm atom of a third unit) forming a square antiprism.     

Polynuclear vanadium complexes from thermal decomposition of [V3O(O2CPh)6(H2O)3]Cl

Solid-state decomposition of [V3O(O2CPh)6(H2O)3]Cl at 300 degrees C followed by alcoholysis of the product gives the new vanadium complexes [V6O6(PhCO2)6(CH3O)6(CH3OH)3] (1), [V6O6(PhCO2)6(C2H5O)6(C2H5OH)3] (2), [V6O6(PhCO2)6(C3H7O)6(C3H7OH)3] (3), [V6O6(PhCO2)6(C4H9O)6(C4H9OH)3] (4) and [V4O4(OCH3)6(O2CPh)2(HOCH3)2] (5). Complexes 2, 3 and 5 have been crystallographically characterised. DC magnetic susceptibility studies on complex shows antiferromagnetic coupling leading to a S = 0 spin ground state.