The molecular organisation in a binary mixture of a strongly polar mesogen (5CB) and a weakly-polar mesogen (ME50.5) is investigated using results of X-ray scattering and density studies. Analysis of the intensity distribution of X-ray scattering has yielded results for orientational order parameters in addition to smectic layer spacings and effective molecular lengths. The results are compared with a mean field theory of the smectic phase. Previously unexplained results for mixtures showing a minimum in the anisotropy of physical properties coincident with a maximum in the nematic/smectic A transition entropy are shown to be consistent with the theory. We conclude that favourable packing of molecules in the injected smectic A phase stabilises the layers but increases the orientational free volume, consistent with a lower orientational order parameter.