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Two unexpected tetranuclear supramolecular boxes, [Zn 4 (L') 4 (CH 3 OH) 2 ]·2CH 3 OH ( 1 ) and [Co 4 (L) 2 (L') 2 (CH 3 OH) 2 ]·acetone ( 2 ), with M 4 (μ 3 -O) 2 (μ 2 -O) 4  core were obtained through reacting coumarin Schiff base H 2 L (H 2 L = 4-hydroxy-3-((2-hydroxyphenyl-imino)-methyl)-2hchrome-2-one) with Zn(OAc) 2 ·4H 2 O and Co(OAc) 2 ·4H 2 O, respectively. Interestingly, the original ligand (H 2 L) has changed into a new structure (H 2 L') in the process of forming single crystals. The structures of  1  and  2  were characterized by X-ray single crystal diffraction.  1  and  2  are tetranuclear structures including four metal centers (Zn(II) or Co(II)), four completely deprotonated ligands (four new (L') 2-  in  1 , two original (L) 2-  and two new (L') 2-  in  2 ), two coordinated methanol molecules and several crystalline solvent molecules. Significantly, due to the action of Zn(II) and Co(II), the original Schiff base H 2 L completely changed from coumarin skeleton to quinoline skeleton to form a new ligand (H 2 L') in  1 , while in  2  half of the ligands H 2 L involved in coordination changed to H 2 L' configuration, the other half maintained the original structure. In  1 , Zn1 ions are six-coordinate octahedral configuration and Zn2 are five-coordinate distorted square-pyramidal configuration with τ = 0.38. In  2 , Co1 are six-coordinate octahedral configuration and Co2 are five-coordinate triangular bipyramidal configuration with τ = 0.66.

journal of coordination chemistry

Synthesis, crystal structure and coordination behaviors of two unexpected tetranuclear Zn(II) and Co(II) supramolecular boxes derived from structural variation of coumarin schiff base ligand