Direct synchrotron x-ray scattering measurements of the orientational order parameter, S, corresponding to the siloxane and hydrocarbon parts of the molecule, smectic layer spacing, and director tilt angle with respect to the smectic-C (SmC) layer normal in the de Vries smectics-A (SmA) and SmC phases of two organosiloxane mesogens are reported. The results reveal that (i) the SmC (tilt) order parameter exponent β = 0.26 ± 0.01 for 2nd order SmA-SmC transition in excellent agreement with the tricritical behavior, (ii) the siloxane and hydrocarbon parts of the molecules are segregated and oriented parallel to the director with different degree of orientational order, and (iii) thermal evolution of the effective molecular length is different in the two phases contrary to the conventional wisdom.