This report illustrates a successful C–H···Hal synthon-directed strategy to promote supramolecular aggregation of molecular luminescent complexes 1–6 into two- or three-dimensional supramolecular architectures. The tin complexes were prepared from the reaction of RnSnHal4–n compounds (R = n-Bu, Ph; Hal = Cl, Br; n = 0, 1) with (C5H4N)HC═N(C6H4)EH Schiff bases by either step-by-step synthesis [E = O (PyNO)] or multicomponent reaction [E = S (PyNS)]. Compounds 1–6 were characterized by IR, Raman, and 1H, 13C, and 119Sn NMR spectroscopic studies as well as by X-ray diffraction studies. In addition, the fluorescent properties of all compounds were also investigated in the solid state and in THF solutions; the emission wavelengths ranged from orange to red (λmax = 591–626 nm). Detailed structural characterization of the supramolecular organization of ordered solids revealed overall 2D and 3D interlinked networks driven by extensive C–H···Hal–Sn (Hal = Cl, Br) weak hydrogen bonds as primordial synthon and furth...