Successfully we prepared crystalline compounds of [Mo36O112(H2O)(16)](8-) ({Mo-36}) anion with various alpha,omega-alkane-diamines (C-n-DA, n = 3-11) aiming at crystal engineering with nanosized building blocks. 2-, 1-, and 0-D frameworks of {M0(36)} were obtained depending on length of alkane moiety of C-n-DA. These frameworks were linked by C-n-DA molecules (or protonated cations) using hydrogen bonds. In the crystalline compounds with C-n-DA cations of n = 3-5 some fraction of the cations were captured in the hollows of {Mo-36}, indicating the ability of {Mo-36} as receptor.