Accurate calculations of vibrational states in singly and doubly substituted ozone molecules are carried out, up to dissociation threshold. Analysis of these spectra reveals noticeable deviations from the statistical factor of 2 for the ratio between the number of states in asymmetric and symmetric ozone molecules. It is found that, for the lower energy parts of spectra, the ratio is less than 2 in the singly substituted ozone molecules, but it is more than 2 in the doubly substituted ozone molecules. However, the upper parts of spectra, just below dissociation thresholds, exhibit a different behavior. In this energy range, the singly and doubly substituted ozone molecules behave similar, with the ratio of states in asymmetric and symmetric ozone molecules being more than 2 in both cases. This property may contribute to an explanation of the mysterious η-effect in the ozone forming reaction that favors the formation of the asymmetric ozone molecules.