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  • 1
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound, (C6H8N)4[Mo8O26], has been prepared and its crystal structure determined by X-ray crystallography. The compound is triclinic,P¯1,Z=1 witha=10.167(1),b=10.745(1),c=10.027(8) Å,α=85.05(1),β=106.73(3), λ=107.75(1)°,V=999.1(7) Å3,F(000)=748,D x=2.59 andD o=2.61(1) Mg/m3. The [Mo8O26]4− anion shows slight differences in several bond lengths and angles when compared with other related octamolybdates. The planar cations are connected to the polyanions through bifurcated hydrogen bonds. The MoO6 octahedra are distorted and the distortion has been evaluated using three different equations. The spectroscopic study shows that the cations are protonated and the polyanion presents the well-known infrared spectrum for octamolybdates.
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  • 2
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Three new heptamolybdates ofn-alkylammonium have been synthesized, with the general formula: (BH)6[Mo7O24]·3H2O, where B=n-butyl-,n-pentyl-, andn-hexylamine (hereafter abbreviated as BUTMO, PENTMO, and HEXMO, respectively). Crystal structure analyses of these compounds show that all of them are isostructural and crystallize in the monoclinic system, the space group beingP21/n,Z=4. Crystal data for PENTMO are: (C5H14N)6[Mo7O24]·3H2O,a=17.085(2),b=31.344(4),c=11.487(12) Å,β=93.04(3)°,V=6143(6) Å3,F(000)=3288,D x =1.77, D0=1.78(1) Mg·m−3,R=0.059, andR w =0.066 for 5526 observed reflections. Only slight differences in cell dimensions have been observed for these compounds, except for the parameterb which is significantly different in all of them. Thermogravimetric studies show that the compounds contain three water molecules. IR spectra indicate that the organic bases are protonated and the polyanion presents the well-known infrared spectrum for heptamolybdates in the solid state. The structure solution confirms that the compound PENTMO contains discrete [Mo7O24]6− anions, (C5H14N)+ cations, and water molecules, connected through hydrogen bonds; the distinguishing features of the compound PENTMO are its extensive hydrogen bonding. The cations and the water molecules are positioned so as to be able to form hydrogen bonds with either molybdate oxygen atoms or water oxygen atoms. The proposed strong hydrogen bonding interactions appear to stabilize the structure. Some of these hydrogen bonds can play an important role in the possible photochromism of this compound.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 24 (1994), S. 457-464 
    ISSN: 1572-8854
    Keywords: Pentafluorophenyl rings ; “ipso” effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The variance in the geometry of pentafluorophenyl rings bonded to metals of the fourth, fifth and sixth rows of the Periodic Table has been analyzed from the data present in the literature. The application of univariate and bivariate analysis to internal coordinates shows that the major variation corresponds to bond angles, specially to those near to the substitution. This effect (“ipso” effect) seems to be related to the Pauling's electronegativity of the metals. Multivariate analysis of these coordinates reveals the existence of three principle effects, the main one of them corresponding to the “ipso” effect and the other two being related with the thermal vibration of the molecule and with the inhomogeneity of the sample. The application of bivariate analysis to symmetry coordinates does not give any correlation between the two orthogonal components describing fully the angular variance.
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