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.