SILVER(I) CARBOXYLATES .13. PREPARATION AND CRYSTAL-STRUCTURES OF SILVER(I) CARBOXYLATES [AG-2(C6H4(CO2)(2))(NH3)(2)], [NH4][AG-5(C6H3(CO2)(3))(2)(NH3)(2)(H2O)(2)]CENTER-DOT-H2O AND [NH4][AG(C4H2N2(CO2)(2))]

Two silver ammine complexes with the polyprotic aromatic acids benzene-1,2-diacarboxylic acid (phthalic acid) and benzene-1.3,5-tricarboxylic acid (trimesic acid) have been prepared and their structures determined using single-crystallic X-ray diffraction and infrared spectroscopy. Complex 1, [Ag-2{C6H4(CO2)(2)}(NH3)(2)], is a hydrogen-bonded polymer based on a simple diamminephthalatodisilver(I) species, with an ammonia molecule and a single phthalate carboxylate oxygen bonded to separate silver atoms, giving essentially linear co-ordination [Ag-N 2.116(3), Ag-O 2.134(2) Angstrom, O-AS-N 175.3(1)degrees]. All three ammine hydrogens are involved in intermolecular hydrogen-bonding interactions, giving a chain polymer. Complex 2, [NH4][Ag-5{C6H3(CO2)(3)}(2)(NH3)(2)(H2O)(2)]. H2O, is a two-dimensional sheet polymer based on a pseudo-centrosymmetric S-type trimer unit, linked by the carboxylate groups of two independent trimesate residues [Ag ... Ag 2.928(1), 2.946(1) Angstrom]. The two ammonia molecules are also bonded linearly to two independent silvers [Ag-N 2.141(6), 2.159(7) Angstrom; N-Ag-O 166.1(2). 170.2(2)degrees]. The terminal silvers provide bonding links to adjacent trimesate carboxyl oxygens between the layers while the third trimesate carboxyl group forms conventional centrosymmetric bis[(carboxylato-O,O')silver(I)] dimers [Ag ... Ag 2.847(1), 2.856(4) Angstrom], with water molecules in the axial sites for the dimer. A third compound 3, ammonium silver(I) pyrazine-2,3-dicarboxylate [NH4][Ag{C4H2N2(CO2)(2)}], has also been prepared using a procedure similar to that for 1 and 2. However, unlike them, it has no bonded ammines but has a distorted trigonal-planar co-ordination involving two carboxylate oxygens [Ag-O 2333(6), 2.376(5) Angstrom] and one heteronitrogen [Ag-N 2.249(6) Angstrom], from three separate ligand molecules, giving a polymer structure.