A five-dimensional structural investigation of the misfit layer compound [Bi0.87SrO2]2[CoO2]1.82

Abstract
The structure of the misfit layer compound [Bi_{0.87}SrO_2]_2[CoO_2]_{1.82}, bismuth strontium cobaltite, was determined by single-crystal X-ray diffraction using the five-dimensional superspace-group formalism. This composite crystal, of monoclinic symmetry, is composed of two subsystems exhibiting incommensurate periodicities along b, the binary axis direction. The first composite part [Bi_{0.87}SrO_2] displays an intrinsic modulation of planar monoclinic type characterized by the wavevector {\bf q}{^*} = 0.293 {\bf a}{^*}+0.915 {\bf c}{^*}. The second composite part [CoO_2] shows two different centered lattice variants. The structure of the misfit layer crystal can be described as an alternation along c of distorted rock-salt-type slabs, formed from [BiO] and [SrO] layers (first subsystem), and of [CoO_2] layers (second subsystem) displaying a distorted CdI_2-type structure. Two main structural results are obtained. First, as a consequence of the intrinsic modulation, disordered zones, characterized by Bi vacancies, are regularly distributed in the [BiO] layers. Second, strong chemical bonds are implied between the strontium atoms of the first subsystem and the oxygen atoms of the second one.

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