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.

The 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 as PowerPoint slide