Synthesis and structural characterization of adducts of silver(I) oxyanion salts, AgX (X = ClO4, NO3), with Ph2E(CH2)xEPh2 (‘dpex’; E = P, As; x = 1–3) and oligodentate aromatic N-bases derivative of 2,2′-bipyridyl, ‘L’, AgX:dpex:L (2:1:1) or (1:1:1)

Six new adducts of silver(I) perchlorate and nitrate, AgX, with N,N′(,-N″)-oligodentate ligands L, derivative of 2,2′-bipyridyl, together with Ph2E(CH2)xEPh2 (≡‘dpex’), are reported and characterized by spectroscopic and structural studies. Two different stoichiometries were found: AgNO3:dpex:‘tpy’ (2:1:1), (‘tpy’ = 2,2′:6′,2″-terpyridyl; 1: dpex = ‘dppm’ (Ph2PCH2PPh2); 2: dpex = ‘dpam’ (Ph2AsCH2AsPh2); 3: dpex = ‘dppp’ (Ph2P(CH2)3PPh2)) and AgClO4:dpex:L (1:1:1), (4: dpex = ‘dpae’ (Ph2As(CH2)2AsPh2), L = tpy); 5: dpex = dppp; L = ‘phen’ (1,10-phenanthroline); 6: dpex = dppp; L = ‘dmp’ (2,9-dimethyl,1,10-phenanthroline)). In AgNO3:dpem:tpy (2:1:1) (1,2), tpy acts as a bridging bis(chelate), the central pyridine donor in ‘crevice’ coordination mode: [(ONO2)Ag(E-dpem-E′)(N,N′-tpy-N′,N″)Ag(O2NO)]. A further bridging tpy is found in tetranuclear AgNO3:dppp:tpy (2:1:1)2 (3), in which the wrapping of a centrosymmetric Ag(μ-ONO2)2Ag kernel by P-dppp-P′ to form [Ag(μ-ONO2)2(P-dppp-P′)2Ag] is pre-empted by the insertion of (Agtpy) into one of the potential Ag–P bonds of each ligand, the third pyridine of the bidentate tpy bridging to a kernel silver atom. AgClO4:dpae:tpy (1:1:1)(∞∣∞) (4) is a single-stranded polymer (⋯Ag(tpy)(As-dpae-As′)Ag(tpy)⋯)(∞∣∞), while AgClO4:dppp:L (1:1:1)2 (5,6) are dimers of the form [LAg(P-dppp-P′)2AgL].