A novel three-dimensional tetranuclear Co coordination polymer with water hexamers based on the V-shaped tetracarboxylate ligand 4-(2,4-dicarboxylatophenoxy)phthalate.

A new coordination polymer (CP), namely, poly[[diaquatris[μ-1,4-bis(1H-imidazol-1-yl)benzene]bis[μ-4-(2,4-dicarboxylatophenoxy)phthalato]tetracobalt(II)] hexahydrate], {[Co(CHO)(CHN)(HO)]·6HO}, has been synthesized by solvothermal reaction. The CP was fully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. It presents a three-dimensional (3D) structure based on tetranuclear Co secondary building units (SBUs) with a tfz-d net and point symbol (4)(4·6·8). The 4-(2,4-dicarboxyphenoxy)phthalic acid (Hdcppa) ligands are completely deprotonated and link {Co(COO)} SBUs into two-dimensional (2D) layers. Furthermore, adjacent layers are connected by 1,4-bis(1H-imidazol-1-yl)benzene (bib) ligands, giving rise to a 3D supramolecular architecture. Interestingly, there are numerous elliptical cavities in the CP where isolated unique discrete hexameric water clusters have been observed. The results of thermogravimetric and magnetic analyses are described in detail.