Article ID Journal Published Year Pages File Type
1334108 Journal of Solid State Chemistry 2005 8 Pages PDF
Abstract

A new Ca6.3Mn3Ga4.4Al1.3O18 compound has been prepared by solid state reaction in a dynamic vacuum of 5×10−6 mbar at 1200 °C. The crystal structure of Ca6.3Mn3Ga4.4Al1.3O18 was studied using X-ray powder diffraction (a=15.07001(5)Å, SG F  432, Z=8Z=8, RI=0.031RI=0.031, RP=0.068RP=0.068), electron diffraction and high resolution electron microscopy. The Ca6.3Mn3Ga4.4Al1.3O18 structure can be described as a tetrahedral [(Ga0.59Mn0.24Al0.17)15O30]18.24− framework stabilized with embedded [(Ca0.9Mn0.1)14MnO6]18.24+ polycations, which consists of an isolated MnO6 octahedron surrounded by a capped cube of (Ca0.9Mn0.1) atoms. The Ca6.3Mn3Ga4.4Al1.3O18 structure is related to the structure of Ca7Zn3Al5O17.5, but appears to be significantly disordered due to the presence of two orientations of oxygen tetrahedra around the cationic 0,0,0 and x,x,x   (x≈0.17,0.15) positions in a random way according to the F432 space symmetry. The analogy between the Ca6.3Mn3Ga4.4Al1.3O18 crystal structure and the structure of the “fullerenoid” Sr33Bi24+δAl48O141+3δ/2 oxide is discussed. Ca6.3Mn3Ga4.4Al1.3O18 adopts a Curie–Weiss behavior of χ(T  ) above T≈50K with a Weiss temperature Θ=-60K and μeff=10.57μB per formula unit. At lower temperatures, the χ(T) deviates from the Curie–Weiss law indicating a strengthening of the ferromagnetic component of the exchange interaction.

Graphical abstractOnion-skin-like structure with the Mn atoms located as a central point surrounded by the enclosed O6, (Ca,Mn)14 and (Ga, Al, Mn)42O104 shells.Figure optionsDownload full-size imageDownload as PowerPoint slide

Related Topics
Physical Sciences and Engineering Chemistry Inorganic Chemistry
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