Coordination polymers of transition metals derived from the in situ nucleophilic addition of alcohols to dicyanonitrosomethanide [C(CN)2(NO)]−

•Transition metal promoted nucleophilic addition of methanol and ethanol to dicyanonitrosomethanide (dcnm).•Addition of 4,4′-bipyridine leads to 1D chains or dinuclear complexes.•Hydrogen bonding interactions between chains in the Zn complex leads to three interpenetrating networks with bsn topology.

The transition metal-promoted in situ nucleophilic addition of methanol and ethanol to a nitrile arm of dicyanonitrosomethanide (dcnm) resulted in the formation of cyano[imino(methoxy)methyl]nitrosomethanide (cmnm) and cyano[imino(ethoxy)methyl]nitrosomethanide (cenm) respectively. In the presence of 4,4′-bipyridine (4,4′-bipy), [Ni(cmnm)2(4,4′-bipy)]·½DMF (1), [Ni(cenm)2(4,4′-bipy)]·EtOH (2) and [Zn(cmnm)2(4,4′-bipy)]·2H2O (3) were isolated as 1D chains. When copper ions were used, a dinuclear structure, namely [Cu2(cmnm)4(4,4′-bipy)] (4) was observed. Synthesis of 1, 2 and 4 also required the presence of CeCl3·6H2O. The cmnm ligands in complex 3 display unique coordination modes to the metal ions, namely κ2(N,O)Zn. Finally, the hydrogen bonding in 3 generates three interpenetrating 3D networks with unusual bsn (or β-Sn) net topology.

Graphical abstractThe nucleophilic addition of methanol and ethanol to dicyanonitrosomethanide, followed by addition of 4,4′-bipyridine, leads to the formation of 1D coordination polymers or dinuclear complexes. Hydrogen bonding interactions between chains in the Zn complex leads to three interpenetrating networks with bsn topology.Figure optionsDownload full-size imageDownload as PowerPoint slide