Two-dimensional incommensurately modulated structure of (Sr0.13Ca0.87)2CoSi2O7 crystals

Abstract

The incommensurate structure of (Sr0.13Ca0.87)2CoSi2O7 at room temperature has been determined from single-crystal X-ray diffraction data. The compound has a non-centrosymmetric tetragonal basic cell of a = 7.8743 (4) and c = 5.0417 (2) Å with the space group P4¯21 m. The refinements of the basic structure converged to R = 0.038 for 757 main reflections. The two-dimensional incommensurate structure is characterized by the wavevectors q 1 = 0.286 (3)(a* + b*) and q 2 = 0.286 (3)(−a* + b*), where a*, b* are the reciprocal lattice vectors of the basic structure. With the (3 + 2)-dimensional superspace group P p4mg P4¯21 m , the refinements converged to R = 0.071 for 1697 observed reflections (757 main and 940 satellite reflections). The structure is described in terms of displacement of the atoms, rotation, distortion of CoO4 and SiO4 tetrahedra, and the partial ordering of the Sr and Ca atoms accompanied with the modulation. Correlated evolution of these features throughout the crystal gives rise to various oxygen coordination around Ca/Sr. Comparison of the derived modulated structure to that of Ca2CoSi2O7 clarified that the partial substitution of Ca by large alkaline-earth atoms such as Sr should decrease the distortion of the polyhedra around the cations.