Abstract
Kinetic ordering of anions in Na((ClO 3) 1− x (BrO 3) x ) solid solutions with anomalous birefringence was studied by means of single crystal X-ray diffraction. The crystal structures of the two samples ( x=0.10 and 0.255) cut out from the {100} growth sectors were refined in the ideal space group P2 13 and in two of its subgroups—monoclinic P2 1 and triclinic P1 with R=0.030–0.038. The final choice of monoclinic symmetry was confirmed by the analysis of the diffraction pattern and Cl/Br distribution over the halogen crystallographic sites. The Cl/Br ordering reflects the geometrical difference of these sites with respect to the growth front orientation. The observed optical indicatrix was successfully reproduced in the point-dipole approximation. According to our data and the data of Crundwell et al. (Acta Crystallogr. Sect. B 53 (1997) 189), the degree of ordering increases in the middle of the isomorphous series along with the birefringence. The obtained results confirm the hypothesis of growth dissymmetrization.
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