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A mixed-valence compound Pb2Cu10O4(SeO3)4Cl

The present article reports on the syntheses, crystal structures and luminescence properties of three solvate forms of a zinc(II) complex containing 4-{(E)-[(2-fluorophenyl)imino]methyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (HL). The reaction of zinc(II)acetate with the HL ligand in ethanol and acetonitrile led to the formation of two solvate analogues [Zn(L)(2)]center dot Solv (Solv - ethanol (1) and acetonitrile (2)). The properties of the [Zn(L)(2)]center dot Solv complexes were investigated by UV-Vis absorption and fluorescence emission spectroscopy, and the density functional theory calculations. Bader's topological analysis was performed to investigate the electronic peculiarities of Zn(II) polyhedra and non-covalent interactions within crystal packing of studied solvates. (C) 2018 Elsevier Ltd. All rights reserved.

The present article reports on the syntheses, crystal structures and luminescence properties of three solvate forms of a zinc(II) complex containing 4-{(E)-[(2-fluorophenyl)imino]methyl}-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (HL). The reaction of zinc(II)acetate with the HL ligand in ethanol and acetonitrile led to the formation of two solvate analogues [Zn(L)2]·Solv (Solv – ethanol (1) and acetonitrile (2)). The properties of the [Zn(L)2]·Solv complexes were investigated by UV–Vis absorption and fluorescence emission spectroscopy, and the density functional theory calculations. Bader's topological analysis was performed to investigate the electronic peculiarities of Zn(II) polyhedra and non-covalent interactions within crystal packing of studied solvates., Export Date: 22 October 2018; Article; CODEN: PLYHD; Correspondence Address: Gusev, A.N.; N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of SciencesRussian Federation; Funding details: № 3874, Minobrnauka, Ministry of Education and Science of the Russian Federation; Funding details: № 16-03-00386, RFBR, Russian Foundation for Basic Research; Funding details: SNIC 2017-12-49, Stiftelsen Olle Engkvist Byggmästare; Funding details: 189-0223, Stiftelsen Olle Engkvist Byggmästare; Funding details: CTS 17:514; Funding details: LO1305; Funding text: Authors would like to acknowledge the financial support from the Russian Foundation for Basic Research (project № 16-03-00386) and Ministry of Education and Science of Russian Federation (project № 3874). G.B. and H.A. acknowledge for support to the Carl Tryggers Foundation (Grant No. CTS 17:514 ) and Olle Engkvist Byggmästare foundation (contract No. 189-0223). The quantum–chemical calculations were performed with computational resources provided by the High Performance Computing Center North (HPC2N) which is a Swedish national center for Scientific and Parallel Computing through the project “Multiphysics Modeling of Molecular Materials” SNIC 2017-12-49. IN and ZT acknowledge financial support going from The Ministry of Education, Youth and Sports of the Czech Republic ( LO1305 ). Appendix A. QC 20181126

© 2016 International Union of Crystallography.Vesuvianite containing 5.85 wt% TiO2 from an Alpine-cleft-type assemblage outcropped near Alchuri, Shigar Valley, Northern Areas, Pakistan, has been investigated by means of electron microprobe analyses, gas-chromatographic analysis of H2O, X-ray powder diffraction, single-crystal X-ray structure refinement, 27Al NMR, 57Fe Mössbauer spectroscopy, IR spectroscopy and optical measurements. Tetragonal unit-cell parameters are: a = 15.5326 (2), c = 11.8040 (2) Å, space group P4/nnc. The structure was refined to final R1 = 0.031, wR2 = 0.057 for 11247 I > 2σ(I). A general crystal-chemical formula of studied sample can be written as follows (Z = 2): [8-9](Ca17.1Na0.9) [8]Ca1.0[5](Fe2+ 0.44Fe3+ 0.34Mg0.22) [6](Al3.59Mg0.41) [6](Al4.03Ti2.20Fe3+1.37Fe2+ 0.40) (Si18O68) [(OH)5.84O2.83F1.33]. The octahedral site Y2 is Al-dominant and does not contain transition elements. Another octahedral site Y3 is also Al-dominant and contains Fe2+, Fe3+ and Ti. The site Y1 is split into Y1a and Y1b predominantly occupied by Fe2+ and Fe3+, respectively. The role of the Y1 site in the diversity of vesuvianite-group minerals is discussed.

© 2016 International Union of Crystallography.Vesuvianite containing 5.85 wt% TiO2 from an Alpine-cleft-type assemblage outcropped near Alchuri, Shigar Valley, Northern Areas, Pakistan, has been investigated by means of electron microprobe analyses, gas-chromatographic analysis of H2O, X-ray powder diffraction, single-crystal X-ray structure refinement, 27Al NMR, 57Fe Mössbauer spectroscopy, IR spectroscopy and optical measurements. Tetragonal unit-cell parameters are: a = 15.5326 (2), c = 11.8040 (2) Å, space group P4/nnc. The structure was refined to final R1 = 0.031, wR2 = 0.057 for 11247 I > 2σ(I). A general crystal-chemical formula of studied sample can be written as follows (Z = 2): [8-9](Ca17.1Na0.9) [8]Ca1.0[5](Fe2+ 0.44Fe3+ 0.34Mg0.22) [6](Al3.59Mg0.41) [6](Al4.03Ti2.20Fe3+1.37Fe2+ 0.40) (Si18O68) [(OH)5.84O2.83F1.33]. The octahedral site Y2 is Al-dominant and does not contain transition elements. Another octahedral site Y3 is also Al-dominant and contains Fe2+, Fe3+ and Ti. The site Y1 is split into Y1a and Y1b predominantly occupied by Fe2+ and Fe3+, respectively. The role of the Y1 site in the diversity of vesuvianite-group minerals is discussed.

The Michael addition of diethyl malonate (Michael Donor, MD) to cyclohexenone (Michael Acceptor, MA) catalysed by the mono-lithium salt of (S)- or (R)-BIMBOL in dichloromethane is shown to exhibit biomimetic behavior. A combination of kinetics, spectroscopic studies, synthesis of catalyst analogues, inhibition studies and DFT calculations are used to show that the catalyst activates both components of the reaction and uses a chain of proton transfers to facilitate the deprotonation of diethyl malonate. The initial reaction rate was first order relative to both MA and MD and 0.5 order relative to the catalyst, indicating that an equilibrium exists between monomeric and dimeric forms of the catalyst, with the dimer predominating, but only the monomeric form being catalytically active. This was supported by DOSY 1H NMR experiments. The importance of the Lewis acidic lithium cation in the catalytic step was established by complete inhibition of the reaction by lithium complexing agents. The importance of the number of OH-groups and their relative intramolecular orientation and acidities in the polyol catalyst was shown by studying the relative catalytic activities of catalyst analogues. DFT calculations allowed the relative energies and structures of the likely intermediates on the reaction coordinate to be calculated and indicated that the ionisation of MD was facilitated due to the Lewis acidity of the lithium cation and hydrogen bond formation between deprotonated MD (MD-1) and the OH groups of the BIMBOL moiety. © 2017 The Royal Society of Chemistry.

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim New nickel-based complexes of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) with BF4− counterion or halide co-ligands were synthesized in THF and MeCN. The nickel(I) complexes were obtained by using two approaches: 1) electrochemical reduction of the corresponding nickel(II) precursors; and 2) a chemical comproportionation reaction. The structural features and redox properties of these complexes were investigated by using single-crystal X-ray diffraction (XRD), cyclic voltammetry (CV), and electron paramagnetic resonance (EPR) and UV/Vis spectroscopy. The influence of temperature and solvent on the structure of the nickel(I) complexes was studied in detail, and an uncommon reversible solvent-induced monomer/dimer transformation was observed. In the case of the fluoride complex, the unpaired electron was found to be localized on the dpp-bian ligand, whereas all of the other nickel complexes contained neutral dpp-bian moieties.

© 2015 American Chemical Society. Two new coronene charge transfer complexes with F4-TCNQ of 2:1 and 1:1:1 (solvate with acetonitrile, MeCN) stoichiometry were obtained using crystal growth procedures from the solution and vapor phase. It was shown that mobility of coronene molecules in crystals is more affected by the asymmetry of its surrounding than by the composition and degree of charge transfer and interstack interactions. The combination of X-ray diffraction and electrochemistry in the solid state and a time-resolved one in solution allowed us to clarify the nucleation in solution showing that the formation of 2:1 coronene/F4-TCNQ complexes is thermodynamically preferable. The X-ray single crystal data for pristine coronene showed the crystal structure to be the same as at ambient temperature, raising doubt about the previously reported phase transitions at 140-180 K.

© 2017 American Chemical Society. It was shown that rotational mobility of molecules in crystals is affected by the symmetry of their surroundings. A hypothesis was proposed for the discovered correlation. Three cases are possible for the location of the molecules with respect to the crystallographic symmetry elements: I - the location in a general position; II - the location in special positions without symmetry disordering; III - the location in special positions with symmetry disordering. According to the experimental data, the rotation barrier heights at the location of the molecules in cases I and III are lower than in case II. This fact is explained by the amplitude and p hase shifts of the rotational energy profiles of two parts of the molecule in case I and by increasing the number of minima on the rotation barrier profile at disordering the molecules by symmetry in case III. The way is proposed for lowering the rotational barrier of molecules in crystals.

© 2017 American Chemical Society. It was shown that rotational mobility of molecules in crystals is affected by the symmetry of their surroundings. A hypothesis was proposed for the discovered correlation. Three cases are possible for the location of the molecules with respect to the crystallographic symmetry elements: I - the location in a general position; II - the location in special positions without symmetry disordering; III - the location in special positions with symmetry disordering. According to the experimental data, the rotation barrier heights at the location of the molecules in cases I and III are lower than in case II. This fact is explained by the amplitude and p hase shifts of the rotational energy profiles of two parts of the molecule in case I and by increasing the number of minima on the rotation barrier profile at disordering the molecules by symmetry in case III. The way is proposed for lowering the rotational barrier of molecules in crystals.

© 2015 American Chemical Society. Two new coronene charge transfer complexes with F4-TCNQ of 2:1 and 1:1:1 (solvate with acetonitrile, MeCN) stoichiometry were obtained using crystal growth procedures from the solution and vapor phase. It was shown that mobility of coronene molecules in crystals is more affected by the asymmetry of its surrounding than by the composition and degree of charge transfer and interstack interactions. The combination of X-ray diffraction and electrochemistry in the solid state and a time-resolved one in solution allowed us to clarify the nucleation in solution showing that the formation of 2:1 coronene/F4-TCNQ complexes is thermodynamically preferable. The X-ray single crystal data for pristine coronene showed the crystal structure to be the same as at ambient temperature, raising doubt about the previously reported phase transitions at 140-180 K.