Crystallisation of simple cyanoruthenate complex anions [Ru(NN)(CN)(4)](2) (NN = 2,2'-bipyridine or 1,10-phenanthroline) in the presence of Lewis-acidic cations such as Ln(III) or guanidinium cations results, in addition to the expected [Ru(NN)(CN)(4)](2) salts, in the formation of small amounts of salts of the dinuclear species [Ru-2(NN)(2)(CN)(7)](3). These cyanide-bridged anions have arisen from the combination of two monomer units [Ru(NN)(CN)(4)](2) following the loss of one cyanide, presumably as HCN. The crystal structures of [Nd(H2O)(5.5)][Ru-2(bipy)(2)(CN)(7)] center dot 11H(2)O and [Pr(H2O)(6)][Ru-2(phen)(2)(CN)(7)] center dot 9H(2)O show that the cyanoruthenate anions form Ru-CN-Ln bridges to the Ln(III) cations, resulting in infinite coordination polymers consisting of fused Ru(2)Ln(2)(mu-CN)(4) squares and Ru(4)Ln(2)(mu-CN)(6) hexagons, which alternate to form a one-dimensional chain. In [CH6N3](3)[Ru-2(bipy)(2)(CN)(7)] center dot 2H(2)O in contrast the discrete complex anions are involved in an extensive network of hydrogen-bonding involving terminal cyanide ligands, water molecules, and guanidinium cations. In the [Ru-2(NN)(2)(CN)(7)](3) anions themselves the two NN ligands are approximately eclipsed, lying on the same side of the central Ru-CN-Ru axis, such that their peripheries are in close contact. Consequently, when NN = 4,4'-Bu-t(2)-2,2'-bipyridine the steric bulk of the t-butyl groups prevents the formation of the dinuclear anions, and the only product is the simple salt of the monomer, [CH6N3](2)[Ru((t)Bu(2)bipy)(CN)(4)] center dot 2H(2)O. We demonstrated by electrospray mass spectrometry that the dinuclear by-product [Ru-2(phen)(2)(CN)(7)](3) could be formed in significant amounts during the synthesis of monomeric [Ru(phen)(CN)(4)](2) if the reaction time was too long or the medium too acidic. In the solid state the luminescence properties of [Ru-2(bipy)(2)(CN)(7)](3) (as its guanidinium salt) are comparable to those of monomeric [Ru(bipy)(CN)(4)](2), with a (MLCT)-M-3 emission at 581 nm
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