Nitrogen Base Adducts with Silver(I) <i>p</i>-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) <i>p</i>-Toluenesulfonate

Abstract

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 (C 14 H 14 Ag 2 O 6 S 2 ) are monoclinic, space group P 2 1 / a, Z = 2, with a = 8.596(3) Å, b = 6.0330(4) Å, c = 15.363(4) Å, and β = 93.03(1)°. 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 AgO 4 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 (C 12 H 12 AgNO 3 S): AgN 2 O 2 centers] or discretely dimeric [ 3 (C 34 H 38 Ag 2 N 8 O 6 S 2 ) and 6 (C 42 H 42 Ag 2 N 4 O 14 S 2 ): both AgN 2 O 2 ] 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 P 2 1, Z = 2, with a = 9.1237(8) Å, b = 5.553(1) Å, c = 12.439(1) Å, and β = 91.182(8)°. For 3, crystals are triclinic, space group P 1̄, Z = 1, with a = 8.635(3) Å, b = 10.434(3) Å, c = 11.138(3) Å, α = 104.89(2), and β = 90.20(2)°, γ = 99.94(2)°. For 6, crystals are monoclinic, space group P 2 1 / a, Z = 4, with a = 8.006(2) Å, b = 31.675(8) Å, c = 8.803(2) Å, and β = 104.413(9)°. 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, C 11 H 12 AgN 3 O 3 S) (trigonal planar AgON 2 repeat) or a pyrimidine-linked, sulfonate-bridged eight-membered cyclic dimer unit, in which the tetrahedral Ag 2 O 2 N 2 centers incorporate an additional unidentate pyrimidine ( 5, C 32 H 41 Ag 2 N 9 O 6 S 2 ). For 4, crystals are monoclinic, space group P 2 1 / n, Z = 4, with a = 6.535(2) Å, b = 7.3440(8) Å, c = 26.13(1) Å, and β = 90.44(1)°: For 5, crystals are monoclinic, space group C 2/ c, Z = 4, with a = 21.312(6) Å, b = 10.650(1) Å, c = 17.565(5) Å, and β = 110.58(1)°. 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.