4-(4-(Nitromethyl)benzylthio)pyridine (abbreviated as L), a ligand bearing 4-pyridyl and nitrobenzene groups, functions as a monodentate ligand and reacts with cobalt(II) chloride and silver(I) perchlorate, leading to new complexes [Co(L)]Cl ( 1) and [Ag(L)]ClO ( 2), respectively. Ligand L and complexes 1 and 2 were characterized through X-ray diffraction, IR spectroscopy and elemental analyses. The coordination geometry of Co(II) and Ag(I) exhibit a slightly-distorted tetrahedron and trigonal planar geometry, respectively. The structures of Ligand L [Monoclinic, P2/c, a = 7.8041(3) Å, b = 20.7401(8) Å, c = 7.2625(3) Å, α = 90°, β = 97.946(3)°, γ = 90°], Complex 1 [Triclinic, P-1, a = 16.2634(14) Å, b = 12.4102(5) Å, c = 13.6324(7) Å, α = 102.733(3)°, β = 95.632(3)°, γ = 99.480(3)°], and Complex 2 [Monoclinic, P2/c, a = 7.6144(6) Å, b = 12.8989(12) Å, c = 28.052(2) Å, α = 90°, β = 92.308(4)°, γ = 90°] reveal several different types of intermolecular interactions, such as Ag···O, π-stacking interactions, and C-H···X (X=O, S, halogen) interactions. Graphical Abstract: Mononuclear complexes [Co(L)]Cl and [Ag(L)]ClO were readily obtained and characterized [L = multidentate 4-(4-(nitromethyl)benzylthio)pyridine], the ligand behavior and the supramolecular architectures of which are observed and discussed. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]