Structural Diversity\nand Dimensionality of Three Cu(II)-dpds‑C<sub>5</sub>O<sub>5</sub><sup>2–</sup> Coordination Polymers Controlled\nby the Coordination Sphere of Cu(II) Centers and the Coordination\nModes of C&

Three supramolecular\narchitectures, [Cu<sub>2</sub>(dpds)<sub>2</sub>(C<sub>5</sub>O<sub>5</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·3H<sub>2</sub>O (<b>1</b>), [Cu­(dpds)­(C<sub>5</sub>O<sub>5</sub>)]·3H<sub>2</sub>O (<b>2</b>), and [Cu<sub>2</sub>(dpds)<sub>2</sub>(C<sub>5</sub>O<sub>5</sub>)<sub>2</sub>]·9H<sub>2</sub>O·C<sub>2</sub>H<sub>5</sub>OH (<b>3</b>) (dpds\n= 4,4′-dipyridyldisulfide and C<sub>5</sub>O<sub>5</sub><sup>2–</sup> (croconate) = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione),\nhave been synthesized and structurally characterized. Compound <b>1</b> contains two crystallographically independent Cu­(II) ions,\nwhich are both distorted octahedral geometry with elongation along\nthe croconate- and H<sub>2</sub>O-bound axial positions and bonded\nwith two N atoms of two dpds, two O atoms of one C<sub>5</sub>O<sub>5</sub><sup>2–</sup>, and two H<sub>2</sub>O molecules. Two\ncrystallographically independent dpds ligands, both adopting the bis-monodentate\nbridging mode, connect two Cu­(II) ions to form a one-dimensional zigzag\nchain-like coordination polymer. In <b>2</b> and <b>3</b>, there are two and three crystallographically independent Cu­(II)\nions, respectively, which are all distorted octahedral geometries\nwith elongation along the croconate-bound axial positions six-coordinated\nand bonded with two N atoms of two dpds ligands in cis- or/and trans-forms\nand four O atoms of two C<sub>5</sub>O<sub>5</sub><sup>2–</sup> ligands. The dpds ligands in <b>2</b> and <b>3</b> all\nadopt the bis-monodentate bridging mode, and the C<sub>5</sub>O<sub>5</sub><sup>2–</sup> ligands act as bridging ligands with\nbridging bis-bidentate through three C<sub>5</sub>O<sub>5</sub><sup>2–</sup> oxygen atoms in <b>2</b> and bridging bis-bidentate\nthrough four adjacent C<sub>5</sub>O<sub>5</sub><sup>2–</sup> oxygen atoms in <b>3</b>, respectively, linking the Cu­(II)\nions to generate a two-dimensional layered and a three-dimensional\nmetal–organic framework, respectively. The structural diversity\nand dimensionality observed in <b>1</b>–<b>3</b> may be attributed to the cis- or/and trans-coordination sphere of\nCu­(II) centers with two dpds ligands and the coordination modes of\ncroconate ligands. Thermal stability and in situ temperature-dependent\nstructural variations of <b>1</b>–<b>3</b> have\nbeen verified by thermogravimetric analysis and powder X-ray diffraction\nmeasurements. Compounds <b>1</b> and <b>3</b> both exhibit\nwater vapor capture behaviors with hysteresis isotherms.