Coordination chemistry of nitrile-functionalized mixed thia-aza macrocycles [9]aneN 2 S and [9]aneNS 2 towards silver(I).

The coordination chemistry towards silver(I) of the small-ring macrocycles [9]aneN 2 S (1-thia-4,7-diazacyclononane) and [9]aneNS 2 (1,4-dithia-7-azacyclononane) incorporating nitrile-functionalized pendant arms is considered both in the presence and the absence of exogenous bridging ligands. The aim is to understand the influence of the number and length of the pendant arms on the nuclearity and dimensionality of the resulting complexes. The X-ray crystal structures of the complexes bis[4,7-bis(cyanomethyl)-1-thia-4,7-diazacyclononane-κ 3 N,N',S]silver(I) tetrafluoridoborate, [Ag(C 10 H 16 N 4 S) 2 ]BF 4 or [Ag(L 1 ) 2 ]BF 4 , [4,7-bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane-κ 3 N,N',S](thiocyanato-κS)silver(I), [Ag(C 12 H 20 N 4 S)(NCS)] or [Ag(L 2 )(SCN)], and μ-thiocyanato-κ 2 S:S-bis{[7-(2-cyanoethyl)-1,4-dithia-7-azacyclononane-κ 3 N,S,S']silver(I)} tetrafluoridoborate, [Ag 2 (C 9 H 16 N 2 S 2 ) 2 (SCN)]BF 4 or [Ag 2 (L 3 ) 2 (μ-SCN)]BF 4 , are discussed in relation to analogous compounds in the literature.