Synthesis and crystal structures of heterometallic AgI/FeII coordination polymers:: (Me3PhN)2[Ag2Fe(SCN)6], (Me3PhN)6]Ag6Fe3(ECN)18] (E = S, Se) and (Me3PhN)4[Ag2Fe(SCN)8]

The reaction of AgSCN with (Me3PhN)(3)[Fe(NCS)(6)] in DMF yields two-dimensional polymeric, heteronuclear complexes (Me3PhN)(2)[Ag2Fe(SCN)(6)] (1) and (Me3PhN)(6)[Ag6Fe3(SCN)(18)] (CH2Cl2DMF)-D-. (2a) with bridging SCN- ligands, whereas additional (Me3PhN)(SCN) leads to (Me3PhN)(4)[Ag2Fe(SCN)8] (3) with a one-dimensional structure. The selenocyanato complex 2b, homologous to 2a, could also be prepared. Single crystal X-ray structure determinations show, that the Ag+ ions in 1 and 2a are coordinated tetrahedrally by four S atoms, in 3 by one N and three S atoms of the bridging SCN- ligands; six N atoms of the SCN- or SeCN- ligands bind to Fe2+ in an octahedral arrangement.