Graham Smith, Brett A. Cloutt, D. Lynch
Jun 10, 1998
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Inorganic Chemistry
Abstract
The complex adducts of silver(I) p-toluenesulfonate, [Ag(pts)], with the nitrogen bases pyridine (1:1), [{Ag-(pts)}(py)] (2), 2-aminopyridine (2:4), [{Ag(pts)}(2-apy)] (3), 2-aminopyrimidine (1:1), [{Ag(pts)}(2-ap)] (4), 4,6-dimethyl-2-aminopyrimidine (2:3), [{Ag(pts)}2(dmap)] (5), and 3-aminobenzoic acid (2:4), [{Ag(pts)}(3-aba)] (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 (CHAgOS) are monoclinic, space group P2/a, Z = 2, with a = 8.596(3) A, b = 6.0330(4) A, c = 15.363(4) A, 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 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 (CHAgNOS): AgNO centers] or discretely dimeric [3 (CHAgNOS ) and 6 (CHAgNOS ): both AgNO] 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, Z = 2, with a = 9.1237(8) A, b = 5.553(1) A, c = 12.439(1) A, and β = 91.182(8)°. For 3, crystals are triclinic, space group P1, Z = 1, with a = 8.635(3) A, b = 10.434(3) A, c = 11.138(3) A, α = 104.89(2), and β = 90.20(2)°, γ = 99.94(2)°. For 6, crystals are monoclinic, space group P2/a, Z = 4, with a = 8.006(2) A, b = 31.675(8) A, c = 8.803(2) A, 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, CHAgNOS) (trigonal planar AgON repeat) or a pyrimidine-linked, sulfonate-bridged eight-membered cyclic dimer unit, in which the tetrahedral AgON centers incorporate an additional unidentate pyrimidine (5, CHAgNOS ). For 4, crystals are monoclinic, space group P2/n, Z = 4, with a = 6.535(2) A, b = 7.3440(8) A, c = 26.13(1) A, and β = 90.44(1)°: For 5, crystals are monoclinic, space group C2/c, Z = 4, with a = 21.312(6) A, b = 10.650(1) A, c = 17.565(5) A, 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)] 7, is also reported, and infrared spectroscopy indicates that it is has both amine-bonded aniline as well as uncoordinated aniline.