First-row transition-metal complexes of the 1-methoxycyclobutenedionate(1-) ion

The synthesis and characterization by single-crystal X-ray crystallography of a series of monomeric first-row transition-metal complexes with the 1-methoxycyclobutenedionate(1-) ligand are described. The isomorphous compounds [M(CH3OC4O3)(2)(H2O)(4)] (M = Mn, Co, Ni, Zn) are C-2 symmetric and crystallize in the monoclinic space group C2/c. The metal atom in each of these complexes is six-coordinate with two cis 1-methoxycyclobutenedionate(1-) ligands, the methoxy substituent being oriented cis with respect to the ligating oxygen atom. The remaining coordination sites are filled by four aqua ligands. Monomers an linked by O-H ... O hydrogen bonds to form arrays of stepped tapes. Hydrolysis of the methoxy group on the ligand occurs during the formation of the copper complex and {[Cu(C4O4)(H2O)(2)]. 0.25H(2)O}(n) is produced. This complex crystallizes in the tetragonal space group P4/n and has a structure similar to, but differing significantly from, those of a series of 3-dimensional cage squarates which have been reported previously.