Synthesis and crystal structure of a new polymer built from a cyano nickel(II) oxa-azamacrocyclic complex

The nickel(II) polymeric complex {[Ni6([22]-HMTADO)3(CN)4][Ni(CN)4] · 5H2O · 8CH3OH}n (III), where H2[22]-HMTADO = 5,5,11,17,17,23-hexamethyl-3,7,15,19- tetraazatricyclo[19,3,1,19,13] hexacosa-1(25),2,7,9,11,13(26),14,19,21,23-decane-25,26-diol, is obtained from methanolic solution of [Ni2([22]-HMTADO)(CN)2] · 0.5H2O (II) by slow evaporation method and characterized by X-ray crystal structure determination. The nickel(II) centers in the oxa-azamacrocyclic complex are bridged by the two phenolate oxygens as well as by CN− and coordinated to carbon and nitrogen atoms derived from the bridging cyano ligand, forming square pyramidal and octahedral geometries, respectively. The mean nonbonded Ni⋯Ni intermetallic separation in the polymeric complex is 3.159 Å.

[Ni2([22]-HMTADO)(CN)2] · 0.5H2O is prepared by reacting [Ni2([22]-HMTADO)(OH2)2]Cl2 · H2O with an aqueous solution of NaCN. The green polymeric single crystal of {[Ni6([22]-HMTADO)3(CN)4][Ni(CN)4] · 5H2O · 8CH3OH}n suitable for X-ray diffraction study is grown from methanolic solution of [Ni2([22]-HMTADO)(CN)2] · 0.5H2O over 2 mon at room temperature.Figure optionsDownload as PowerPoint slide