AbstractAlkyl‐amines with formula CnH2n+1‐NH2 (n=8, 10, 12, 14 and 16), either liquid or solid at room temperature, can form a stripe‐like crystalline matrix with 1.6‐2.1 nm width when in the presence of an external magnetic field, that able to confine the H2dcbp (4,4’‐diacarboxy‐2,2’‐bipyridine) molecules within the stripes interval with stoichiometry of 2:1. This confinement, which can improve the alcohol solubility of H2dcbp remarkably, has facilitated the construction of mononuclear spin‐crossover complex Fe(H2Bpz)2(H2dcbp) (H2Bpz=dihydrobis(1‐pyrazolyl)borate). Thus, the crystalline matrix may provide a convenient method for construction of new hybrid materials derived from H2dcbp and its analogue, through hierarchy control of both the coordination bonding and the hydrogen bonding of H2dcbp at a mild condition.