The complex adducts of silver(I) p-toluenesulfonate, [Ag(pts)], with the nitrogen bases pyridine (1:1), [{Ag(pts)}(py)](n) (2), 2-aminopyridine (2:4), [{Ag(pts)}(2)(2-apy)(4)] (3), 2-aminopyrimidine (1:1), [{Ag(pts)}(2-ap)](n) (4), 4,6-dimethyl-2-aminopyrimidine (2:3), [{Ag(pts)}(2)(dmap)(3)](n) (5), and 3-aminobenzoic acid (2:4), [{Ag(pts)}(2)(3-aba)(4)] (6), have been prepared and their structures, together with that of the parent compound, silver(I) p-toluenesulfonate (1), determined by X-ray diffraction. Crystals of 1 (C14H14Ag2O6S2) are monoclinic, space group P2(1)/a, Z = 2, with a = 8.596(3) Angstrom, b = 6.0330(4) Angstrom, c = 15.363(4) Angstrom, and beta = 93.03(1)degrees. The polymeric structure is based on bis(sulfonato-(O,O') bridged dimers analogous to those found in some of the O,O'-bridged silver(I) carboxylates, these also having pseudo trigonal bipyramidal AgO4 centers. All sulfonate oxygens are utilized in coordination. The structures of the monoheteroaromatic nitrogen donor group adducts (2, 3, and 6) are either polymeric [2 (C12H12AgNO3S) : AgN2O2 centers] or discretely dimeric [3 (C34H38Ag2N8O6S2) and 6 (C42H42Ag2N4O14S2) : both AgN2O2] and can be considered the result of replacement of either one or two oxygen sites about the silver in [Ag(pts)] by nitrogen donors, with subsequent rearrangement about very distorted tetrahedral silver centers. For 2, crystals are monoclinic, space group P2(1), Z = 2, with a = 9.1237(8) Angstrom, b = 5.553(1) Angstrom, c = 12.439(1) Angstrom, and beta = 91.182(8)degrees For 3, crystals are triclinic, space group P (1) over bar, Z = 1, with a 8.635(3) Angstrom, b = 10.434(3) Angstrom, c = 11.138(3) Angstrom, alpha = 104.89(2), and beta = 90.20(2)degrees, gamma = 99.94(2)degrees. For 6, crystals are monoclinic, space group P2(1)/a, Z = 4, with a = 8.006(2) Angstrom, b = 31.675(8) Angstrom, c = 8.803(2) Angstrom, and beta = 104.413(9)degrees. Hydrogen-bonding interactions via the second functional group in both 3 and 6 give additional lattice stability. However, with the bifunctional heteroaromatic pyrimidines, extension of the polymer structures occurs through both ring nitrogens to give either a simple ribbon polymer (4, C11H12AgN3O3S) (trigonal planar AgON2 repeat) or a pyrimidine-linked, sulfonate-bridged eight-membered cyclic dimer unit, in which the tetrahedral Ag2O2N2 centers incorporate an additional unidentate pyrimidine (5, C32H41Ag2N9O6S2) For 4, crystals are monoclinic, space group P2(1)/n, Z = 4, with a = 6.535(2) Angstrom, b 7.3440(8) Angstrom, c = 26.13(1) Angstrom, and beta = 90.44(1)degrees : For 5, crystals are monoclinic, space group C2/c, Z = 4, with a = 21.312(6) Angstrom, b = 10.650(1) Angstrom, c = 17.565(5) Angstrom, and beta = 110.58(1)degrees. Hydrogen bonding is also significant in lattice stabilization in both of these structures. The preparation of an unstable adduct of Ag(pts) with aniline, [{Ag(pts)}(an)(3)] 7, is also reported, and infrared spectroscopy indicates that it is has both amine-bonded aniline as well as uncoordinated aniline.