Anion‐controlled Syntheses and Crystal Structures of a Pair of Novel Azide‐bridged Copper(II) Complexes Constructed from 4‐Chloro‐2‐[(2‐dimethylaminoethylimino)methyl]phenol

A pair of novel azide‐bridged polynuclear copper(II) complexes, [CuL(μ 1,1 ‐N 3 )] n ( 1 ) and [Cu 4 L 2 (CH 3 COO) 2 (μ 1,1 ‐N 3 ) 4 ] ( 2 ) (L = 4‐chloro‐2‐[(2‐dimethylaminoethylimino)methyl]phenolate), have been obtained from the same Schiff base ligand and an identical synthetic procedure using anions of the metal salts as the only independent variable. Complex 1 was synthesized using copper(II) nitrate, while complex 2 was synthesized using the copper(II) acetate as the salt. Both of the complexes show novel supramolecular structures in their crystals as elucidated by X‐ray analyses. The polynuclear complex 1 contains [CuL(μ 1,1 ‐N 3 )] n units as the building blocks, crystallizes in the P bca space group. The tetra‐nuclear complex 2 contains [Cu 4 L 2 (CH 3 COO) 2 (μ 1,1 ‐N 3 ) 4 ] units as the building blocks, crystallizes in the $P{\bar 1}$ space group.