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Two novel silver(I) coordination polymers, [Ag(4BP)(SCN)]n (1) and {(4BPH)+[Ag(SCN)2]−}n (2) (4BP = 4-benzoyl pyridine), have been synthesized. The two complexes were prepared using almost the same reagents, which were AgNO3, 4BP and NH4SCN. The only difference was the presence of 1:1 (v/v) HNO3 in the synthesis of 2. In the two complexes, the Ag(I) has distorted tetrahedral coordination geometry. The structure of both complexes and the involvement of the thiocyanate anion as a linker between the Ag(I) centers were confirmed using single-crystal X-ray diffraction. 4BP participated as a monodentate ligand in the coordination sphere of complex 1, while in 2 it is found protonated (4BP-H)+ and acts as a counter ion, which balances the charge of the anionic [Ag(SCN)2]− moiety. The thiocyanate anion shows different coordination modes in the two complexes. In complex 1, the thiocyanate anion exhibits a µ1,1,3 bridging mode, which binds three Ag(I) ions to build a boat-like ten-membered ring structure leading to a two-dimensional coordination polymer. In 2, there are mixed µ1,1 and µ1,3 bridging thiocyanate groups, which form the one-dimensional polymeric chain running in the a-direction. Several interactions affected the stability of the crystal structure of the two complexes. These interactions were examined using Hirshfeld surface analysis. The coordination interactions (Ag-S and Ag-N) have a great impact on the stability of the polymeric structure of the two complexes. Additionally, the hydrogen-bonding interactions are crucial in the assembly of these coordination polymers. The O...H (10.7%) and C...H (34.2%) contacts in 1 as well as the N···H (15.3%) and S···H (14.9%) contacts in 2 are the most significant. Moreover, the argentophilic interaction (Ag...Ag = 3.378 Å) and π- π stacking play an important role in the assembly of complex 2. [ABSTRACT FROM AUTHOR]