NITROGEN BASE ADDUCTS WITH SILVER(I) P-TOLUENESULFONATE - SYNTHESES AND SINGLE-CRYSTAL X-RAY CHARACTERIZATIONS OF THE ADDUCTS WITH PYRIDINE(1 1), 2-AMINOPYRIDINE (1/2), 2-AMINOPYRIMIDINE (1/1), 4,6-DIMETHYL-2-AMINOPYRIMIDINE (2/3), AND 3-AMINOBENZOIC ACID (1/2) AND THE CRYSTAL-STRUCTURE OF THE PARENT SILVER(I) P-TOLUENESULFONATE/

The complex adducts of silver(I) p-toluenesulfonate, [Ag(pts)], with t he nitrogen bases pyridine (1:1), [{Ag(pts)}(py)](n) (2), 2-aminopyrid ine (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-a ba)(4)] (6), have been prepared and their structures, together with th at of the parent compound, silver(I) p-toluenesulfonate (1), determine d 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 poly meric structure is based on bis(sulfonato-(O,O') bridged dimers analog ous to those found in some of the O,O'-bridged silver(I) carboxylates, these also having pseudo trigonal bipyramidal AgO4 centers. All sulfo nate oxygens are utilized in coordination. The structures of the monoh eteroaromatic nitrogen donor group adducts (2, 3, and 6) are either po lymeric [2 (C12H12AgNO3S): AgN2O2 centers] or discretely dimeric [3 (C 34H38Ag2N8O6S2) and 6 (C42H42Ag2N4O14S2): both AgN2O2] and can be cons idered the result of replacement of either one or two oxygen sites abo ut the silver in [Ag(pts)] by nitrogen donors, with subsequent rearran gement about very distorted tetrahedral silver centers. For 2, crystal s are monoclinic, space group P2(1), Z = 2, with a = 9.1237(8) Angstro m, 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) An gstrom, 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) Angst rom, and beta = 104.413(9)degrees. Hydrogen-bonding interactions via t he second functional group in both 3 and 6 give additional lattice sta bility. However, with the bifunctional heteroaromatic pyrimidines, ext ension of the polymer structures occurs through both ring nitrogens to give either a simple ribbon polymer (4, C11H12AgN3O3S) (trigonal plan ar AgON2 repeat) or a pyrimidine-linked, sulfonate-bridged eight-membe red cyclic dimer unit, in which the tetrahedral Ag2O2N2 centers incorp orate 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) An gstrom, and beta = 110.58(1)degrees. Hydrogen bonding is also signific ant in lattice stabilization in both of these structures. The preparat ion of an unstable adduct of Ag(pts) with aniline, [{Ag(pts)}(an)(3)] 7, is also reported, and infrared spectroscopy indicates that it is ha s both amine-bonded aniline as well as uncoordinated aniline.