The syntheses and the spectroscopic characterization (IR, H-1, C-13 and P-31 NMR, ESI-MS and conductivity studies) of a number of adducts of silver(I) perchlorate and nitrate, AgX, with N,N'(N")-oligodentate ligands L, derivative of 2,2'-bipyridyl, together with Ph2E(CH2)(x)EPh2 ('dpex', x predominantly 1,2 ('dpem', 'dpee') tout also 3,4 ('dppp', 'dppb'), E = P, As) are reported, of stoichiometry AgX:dpex:L (2:1:2), L-2,2'-bipyridyl ('bpy')- 1,10-phenanthroline ('phen'); 2,9-dimethyl, 1,10-phenanthroline ('dmp'); bis(2-pyridyl)amine ('dpa'); 2,2'-biquinolyl ('bq')- 2,2': 6'2"-terpyridyl ('tpy'). For AgClO4:dppm:bpy, phen, dmp, tpy; AgClO4:dpem:phen, dmp, troy; AgNO3:dppm:bpy, bq (2:1:2), the compounds are of the form [LAg(E-dpem-E')AgL]X-2, the pair of Ag-E bonds lying cis/parallel about the ECH2E core, of quasi-C-2 nu, symmetry; for AgClO4:dppm:dpa; AgNO3:dppm:bpy (2:1:2), the Ag-E bonds lie trans, with a cation symmetry (quasi-)2. In AgNO3:dppm, dpam:dmp (2:1:2), loosely coordinated nitrate ions approach one of the silver atoms as unidentate ligands, Ag-E being 'cis': [(O2NO)(dmp)Ag(E-dpem-E')Ag(dpm)](NO3). The majority of [LAg(E-dpex-E')AgL] (dpex = dpee, dpeb) arrays (AgClO4:dppe:bpy, bq, dpa, tmp, tpy; AgClO4:dpae:bpy, bq; AgClO4:dpdae:dmp (E = P, E' = As); AgClO4:dppb:dpa, bq, tpy; AgNO3:dppb:tpy (2:1:2)) are centrosymmetric and trans-oid with close approaches to the silver atoms by oxyanions or solvent (MeCN) molecules; AgClO4:dpae:dmp (2:1:2) is cis-oid, as also are the dppp adducts, AgClO(4:)dppp:dmp, bq (2:1:2). A novel bridging tpy coordination mode is found, whereby pairs of silver atoms are linked eta(2) (sigma,pi) into a single stranded polymer in AgClO4:dppp:tpy (2:1:2), thus [...Ag(P-dppp-P')Ag(mu-N")tpy)(2)...]((infinity vertical bar infinity)) (c) 2006 Elsevier B.V. All rights reserved.