Abstract: | Three polymeric silver(I) complexes with terephthalate anions as counterions or ligands, Ag(pren)]2(tp)·2H2O ( 1 ), Ag(en)]Ag(μ2‐tp)]·H2O ( 2 ), and Ag2(μ4‐tp)(apy)2] ( 3 ) (where pren = 1, 2‐propylenediamine, tp =terephthalate dianion, en = ethylenediamine, and apy = 2‐aminopyridine) were synthesized and characterized by X‐ray single crystal analysis and infrared spectroscopy. 1 crystallizes in the monoclinic space group P211/c with a = 11.3221(5), b = 7.1522(3), c = 14.8128(5)Å, V = 1015.77(7)Å3, β = 122.132(2), and Z = 2. 2 crystallizes in the orthorhombic space group Pnma with a = 9.6144(6), b = 11.3465(7), c = 11.4810(7)Å, V = 1252.5(1)Å3, and Z = 4. 3 crystallizes in the monoclinic space group P21/n with a = 8.2003(5), b = 5.8869(4), c = 18.3769(11)Å, β = 92.593(1), V = 886.2(1)Å3, and Z = 4. Terephthalate dianions are not coordinated to the metal atoms in 1 , but act as a μ2‐bridging ligand in 2 and as a μ4‐bridging ligand in 3 . |