The reaction of 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (tppe) with [Fe(NCBH3)(2)] produced a two-dimensional coordination polymer [Fe(NCBH3)(2)(tppe)](n) (1), which was pillared in an ABAB manner through interlayer multiple [C-H delta+center dot center dot center dot H delta--B] dihydrogen bonds (DHBs) to form a stable porous three-dimensional (3D) supramolecular structure that showed guest-molecule-dependent spin-crossover behaviors.