We evaluated the difference between randomly packed NCs (disordered films), periodic films, and three-dimensional crystals in terms of their lattice structure and interparticle spacing using time-resolved small-angle X-ray scattering (SAXS) technique. The work was performed on nanocrystal solids formed by 7 nm PbS nanocrystals capped with oleic acid. We have found that interparticle spacing in faceted three-dimensional crystals is similar to 25% smaller as compared with three-dimensional films formed by solvent evaporation. We showed that interparticle spacing in faceted three-dimensional crystals is significantly smaller than the length of a fully extended molecule of oleic acid, and hence, full interdigitation of molecules from neighboring particle is doubtful. Also we demonstrated that postpreparative mild thermal treatment allows further manipulation of interparticle spacing.