Flexible square supramolecular rings with hydrogen-bonded bushing in solid-state oxalurate complexes: versatility of the oxalurate ligand in covalent and noncovalent binding.

Isotypic pseudooctahedral complexes of Co, Ni, and Cu with two chelating oxalurate ligands and two water molecules, trans-[M(oxalurate)(2)(H(2)O)(2)], have been synthesized and isolated by a novel progressive crystallization technique. Diffraction analyses reveal that the three complexes form isotypic solid-state structures in which the molecular connectivity and complex network of noncovalent interactions are qualitatively identical throughout the series. The oxalurate groups form unbounded chains through two different self-recognition patterns-a typical DA-AD motif and an unusual DDA'-A'DD form (D = hydrogen bond donor, A' = double acceptor). The unsymmetrical oxalurate group possesses the topological properties necessary to form aggregates of higher symmetry, and the "M(oxalurate)(2)" fragments form a rhombic 2-D motif with hydrogen-bonded corners and with hydrogen-bond acceptors directed to the inside of the cyclic aggregate. The 2-D net is stacked to form a channeled 3-D structure, in which the coordinated aqua ligands form the principal interlayer interactions. The slanted channels are occupied by the axial waters and by waters of crystallization, which are hydrogen bonded to the channel walls to form an ordered bushing. The extensive 3-D hydrogen-bonded superstructure is flexible enough to accommodate the distortion produced by the Jahn-Teller effect in the copper compound without requiring a qualitative structural change. The bonds affected by Jahn-Teller distortion in the Cu complex [Cu-O = 2.3788(15) A] are significantly longer than their analogues in the Co and Ni complexes [Co-O = 2.175(2), Ni-O = 2.094(9) A].