It is considered practically impossible to differentiate between oxygen and fluorine atoms by X-ray diffraction in disordered structures of oxyfluoride compounds due to the similarity of their ionic radii and diffusion factors. Indeed, many transition metal oxyfluoride compounds containing polar pseudo-octahedral MOxF6–x (x = 1-3) anions form crystal structures without any fluorine-oxygen (F/O) ordering owing to a large number of local anion configurations. Because of this static disorder, it is impossible to determine the positions of O and F atoms and find the real geometry of the polyhedron. However, this becomes possible in the case of dynamic disorder of oxyfluoride anions when the central atom is displaced from the center of the octahedron toward a vertex, edge, or face (depending on the number of oxygen atoms in the polyhedron), which enables the identification of O and F atoms owing to inherent differences between M–O and M–F bonding. On cooling, such compounds undergo phase transitions of the order–disorder type with substantial changes in the entropy. The examples of static and dynamic orientational disorder in oxyfluoride compounds of d0 transition metals are given. 相似文献
4-Amino-1,2,4-triazolium hexafluoridoniobate(V) and hexafluoridotantalate(V) (C2H5N4)MF6 (M = Nb, Ta) crystallizing in the monoclinic system (space group P21/n) are synthesized for the first time and their crystal structures and spectroscopic features are studied by single crystal X-ray diffraction and 1H and 19F NMR spectroscopy. The crystal structures of isostructural (C2H5N4)MF6 compounds are formed of octahedral complex [MF6]– anions (M = Nb, Ta) and monoprotonated heterocyclic 4-amino-1,2,4-triazolium cations (C2H5N4)+ organized in a three-dimensional structure via N–H···F and N–H···N hydrogen bonds. The character and types of ion motions in the fluoride sublattice of (C2H5N4)MF6 are determined in a wide temperature range. 相似文献
The single-crystal structure of cooperite, a natural platinum sulfide PtS, is studied by X-ray diffraction supported by high-resolution scanning transmission electron microscopy and X-ray spectrum microanalysis. It is found that, in addition to the main reflections corresponding to the known tetragonal cell (a = 3.47 and c = 6.11 Å; space group P42/mmc), many weak reflections with intensities I ≤ 60σ(I) are clearly observed. These reflections fit the tetragonal cell (space group I4/mmm) with doubled parameters. In structures with small (P42/mmc) and large (I4/mmm) cells, the S atoms occupy statistically two special positions. It is shown that the chemical composition of the cooperite crystals deviates from the stoichiometric composition: sulfur-deficient specimens predominate. 相似文献
Antimony(III) fluoride complexes with compositions (NH4)3Sb4F15(I) and Cs3Sb4F15(II) are structurally characterized. Crystals Iare triclinic: a= 8.317(3) Å, b= 10.419(6) Å, c= 10.826(3) Å, = 63.71(4)°, = 73.24(3)°, = 77.42(5)°, Z= 2, calcd= 3.42 g/cm3, exp= 3.45 g/cm3, space group P
, R= 0.051; crystals IIare monoclinic: a= 8.079(2) Å, b= 29.116(8) Å, c= 8.162(2) Å, = 117.08(2)°, Z= 4, calcd= 4.549 g/cm3, exp= 4.50 g/cm3, space group P21/c, R= 0.036. Structure Iis composed of SbF4E and SbF5E polyhedra combined into tetranuclear chains; crystals IIconsist of SbF4E polyhedra, two of which form a dimer Sb2F7E2, while the other two are isolated (E is the antimony lone electron pair). 相似文献
The technique of studying the synchrotron radiation scattering on single crystals over wide temperature range using an original miniature device for applying an electric field to a sample is described. A specific feature of the device is the possibility of its application with various heating and cooling systems. The technique was used at BM01 beamline at the European Synchrotron Radiation Facility (ESRF) for the study of the influence of electric field on the processes of structural transformation in lead zirconate–titanate single crystal with a low titanium concentration. The efficiency of the technique proposed in this work is demonstrated and the results of the preliminary analysis of the results are presented.
The crystal structure of acrylamide is re-determined by single crystal X-ray diffraction (133(1) K, BRUKER SMART 1000 CCD, a = 8.228(1) Å, b = 5.759(1) Å, c = 9.760(1) Å, β = 120.04(1)°, V = 400.3(1) Å,3, space group P21/c, Z = 4, R = 0.0543 for 867 reflections). In the structure strong hydrogen bonds N-H...O join the molecules of C3H5NO into bi-molecular layers that make C...C molecular contacts. It is demonstrated that the process of solid phase polymerization of acrylamide should proceed through the cleavage of double bonds C(1)=C(2) in the monomers and formation of bonds C(1)-C(1) and C(2)-C(2) between the closest carbon atoms of different layers. 相似文献