Cation ordering and structural variations with temperature in MgAl2O4spinel: An X-ray single-crystal study

2000 ◽  
Vol 85 (9) ◽  
pp. 1164-1171 ◽  
Author(s):  
Giovanni B. Andreozzi ◽  
Francesco Princivalle ◽  
Henrik Skogby ◽  
Antonio Della Giusta
2002 ◽  
Vol 58 (2) ◽  
pp. 191-197 ◽  
Author(s):  
O. Perez ◽  
A. C. Masset ◽  
H. Leligny ◽  
G. Baldinozzi ◽  
D. Pelloquin ◽  
...  

The structure of the m = 2 tubular compound Bi4Sr12Co8O30−δ, bismuth strontium cobalt oxide, was determined by single-crystal X-ray diffraction. This phase of orthorhombic symmetry exhibits a very strong tetragonal pseudosymmetry. The structure consists of 90°-oriented Bi2Sr2CoO6+δ slices, four Co atoms wide, forming [Sr4Co4O13]∞ pillars at their intersection. The Co atoms in these pillars form four corner-sharing CoO5 bipyramids. In the resulting [Co4O13] cluster, an anionic disorder is evidenced and discussed. Then, an accurate description of the particular structure of the pillars is given. Finally, a comparison with the Mn tubular compound Bi3.6Sr12.4Mn8O30−δ is carried out.


2009 ◽  
Vol 73 (6) ◽  
pp. 1033-1050 ◽  
Author(s):  
L. A. Groat ◽  
E. S. Grew ◽  
R. J. Evans ◽  
A. Pieczka ◽  
T. S. Ercit

AbstractHoltite, approximately (Al,Ta,□)Al6(BO3)(Si,Sb3+,As3+)Σ3O12(O,OH,□s)Σ3, is a member of the dumortierite group that has been found in pegmatite, or alluvial deposits derived from pegmatite, at three localities: Greenbushes, Western Australia; Voron'i Tundry, Kola Peninsula, Russia; and Szklary. Lower Silesia, Poland. Holtite can contain >30 wt.% Sb2O3, As2O3, Ta2O5, Nb2O5, and TiO2 (taken together), but none of these constituents is dominant at a crystallographic site, which raises the question whether this mineral is distinct from dumortierite. The crystal structures of four samples from the three localities have been refined to R1 = 0.02—0.05. The results show dominantly: Al, Ta, and vacancies at the Al(l) position; Al and vacancies at the Al(2), (3) and (4) sites; Si and vacancies at the Si positions; and Sb, As and vacancies at the Sb sites for both Sb-poor (holtite I) and Sb-rich (holtite II) specimens. Although charge-balance calculations based on our single-crystal structure refinements suggest that essentially no water is present, Fourier transform infrared spectra confirm that some OH is present in the three samples that could be measured. By analogy with dumortierite, the largest peak at 3505-3490 cm-1 is identified with OH at the O(2) and O(7) positions. The single-crystal X-ray refinements and FTIR results suggest the following general formula for holtite: Al7-[5x+y+z]/3 (Ta,Nb)x□[2x+y+z]\3,BSi3-y(Sb,As)yO18-y-z(OH)z, where x is the total number of pentavalent cations, y is the total amount of Sb + As, and z ⩽ y is the total amount of OH. Comparison with the electron microprobe compositions suggests the following approximate general formulae Al5.83(Ta,Nb)0.50□0.67BSi2.50(Sb,As)0.50O17.00(OH)0.50 and Al5.92(Ta,Nb)0.25□0.83BSi2.00(Sb,As)1.00O16.00(OH)1.00 for holtite I and holtite II respectively. However, the crystal structure refinements do not indicate a fundamental difference in cation ordering that might serve as a criterion for recognizing the two holtites as distinct species, and anion compositions are also not sufficiently different. Moreover, available analyses suggest the possibility of a continuum in the Si/(Sb + As) ratio between holtite I and dumortierite, and at least a partial continuum between holtite I and holtite II. We recommend that use of the terms holtite I and holtite II be discontinued.


2002 ◽  
Vol 14 (5) ◽  
pp. 929-934 ◽  
Author(s):  
Luca Bindi ◽  
Oleg G. Safonov ◽  
Yuriy A. Litvin ◽  
Leonid L. Perchuk ◽  
Silvio Menchetti

1999 ◽  
Vol 18 (8) ◽  
pp. 1019-1032 ◽  
Author(s):  
Mohamed Selkti ◽  
Rima Kassab ◽  
Hélène Parrot Lopez ◽  
Françoise Villain ◽  
Colette de Rango

2006 ◽  
Vol 61 (1) ◽  
pp. 23-28 ◽  
Author(s):  
Vasyl’ I. Zaremba ◽  
Yaroslav M. Kalychak ◽  
Mariya V. Dzevenko ◽  
Ute Ch. Rodewald ◽  
Birgit Heying ◽  
...  

The rare earth-cobalt-indides RE14Co3In3 (RE = Y, Tb, Dy, Ho, Er) were prepared in polycrystalline form from the elements by arc-melting. Small single crystals were grown through a special annealing sequence. The compounds were investigated on the basis of X-ray powder and single crystal data: Lu14Co2In3 (Gd14Co3In2.7) type, P42/nmc, Z = 4, a = 959.0(1), c = 2319.1(5) pm, wR2 = 0.055, 2289 F2 values, 65 variables for Y13.90Co2.99In3.02, a = 953.8(1), c = 2315.8(5) pm, wR2 = 0.108, 2357 F2 values, 65 variables for Tb13.92Co3.01In2.92, a = 949.24(3), c=2296.5(1) pm, wR2= 0.129, 2518 F2 values, 65 variables for Dy13.90Co2.97In2.95, a=946.3(1), c = 2289.0(5) pm, wR2 = 0.099, 2297 F2 values, 64 variables for Ho14Co2.80In2.89, and a = 941.0(1), c = 2274.2(5) pm, wR2 = 0.140, 2450 F2 values, 65 variables for Er13.83Co2.88In3.10. All RE14Co3In3 indides show a small degree of In/Co mixing (between 7 and 16% Co) on the 4c In1 site and defects on the 8g Co1 positions (between 84 and 95% Co). Except for the holmium compound, the RE14Co3In3 intermetallics also reveal RE/In mixing on the 4c RE1 sites, leading to the refined compositions. The seven crystallographically independent RE sites have between 9 and 10 nearest RE neighbors. The RE14Co3In3 structures consist of a complex intergrowth of rare earth based polyhedra. Both cobalt sites have a distorted trigonal-prismatic rare earth coordination. An interesting feature is the In2-In2 dumb-bell with an In2-In2 distance of 300 pm (for Ho14Co2.80In2.89). The crystal chemistry of the RE14Co3In3 indides is discussed.


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