Superspace description of NaCa4Nb5O17 (a perovskite-related compound of the type AnBnO3n+2) as a modulated layered structure.
The recently determined structure of NaCa(4)Nb(5)O(17) is reanalyzed within the superspace framework. The material follows the general features of the superspace model proposed for the perovskite-related compounds of the general formula A(n)B(n)O(3n+2) [Elcoro et al. (2001). Acta Cryst. B57, 471-484]. It can be described as a commensurate modulated structure with discontinuous atomic domains given by occupational crenel functions. These atomic domains automatically introduce the layered configuration of the actual structure in real space. However, the displacive modulations follow a quite different pattern from that observed in the Sr(n)(Nb,Ti)(n)O(3n+2) series, discussed in the above-mentioned reference. The superspace group relevant in this new case has been identified through a systematic search of all the possible groups and a comparison of the resulting superspace embeddings of the experimental three-dimensional structure. Being a commensurate structure, the fundamental ambiguity of the superspace description was broken by choosing the highest possible symmetry that yields smooth displacive atomic modulations and hence minimizes the number of parameters. The efficiency of the proposed superspace model is demonstrated with a new refinement of the structure. Assuming the model's general relevance, symmetry properties for the whole [Ca,Na](n)Nb(n)O(3n+2) series are predicted.
On the structure and symmetry of incommensurate phases. A practical formulation
The structural description, symmetry and diffraction properties of incommensurate modulated phases are revised using a real-space framework. The superspace formalism usually employed is reformulated using a practical description where no multidimensional geometrical constructions are needed. The incommensurate structural distortion is described in terms of 'atomic modulation functions' where the internal space is only considered as a continuous label for the cells of the non-distorted structure. Hence, no atomic positions or thermal tensors in a multidimensional space are defined. By this means and with the introduction of the concept of 'atomic modulation factors' a general expression for the structure factor is proposed which constitutes a direct generalization of the standard expression for a commensurate structure. The concept of superspace symmetry is reduced in this approach to a simple relation between the defined atomic modulation functions, which can be directly translated by means of the structure-factor expression into the symmetry and extinction rules of the diffraction diagram. The advantages of superspace formalism in the analysis of commensurate modulated phases are also discussed. The use of superspace groups for describing the symmetry of superstructures, contrary to some recent claims, does not formally reduce the number of structural parameters but may often allow some of them to be neglected.
Incommensurability in crystals
Abstract The aim of this review is to present aperiodic crystals from a unifying point of view, showing why it is justified to call them crystals, despite the lack of a three-dimensional lattice periodicity, and to discuss in what sense they differ from periodic crystals in structure, symmetry and other physical properties. The extension of the concept of crystal has been based, during the last two decades, on investigation of incommensurate crystal phases. Among these, the most important ones are the modulated crystals. Their crystallographic nature, already apparent in the diffraction pattern, could be made explicit on the symmetry level by embedding in a higher-dimensional Euclidean space. The recent discovery of quasicrystal phases (representing a fairly different class of aperiodic crystals than the modulated ones) can also be approached in a similar way. Furthermore, it now appears that another class of incommensurate crystals, the so-called composite structures, represents a kind of intermediate ca...