Herein, four different coordination networks were isolated and structurally characterized by combining two aminocarboxylate ligands, 4,4 '-[biphenyl-4,4 '-diylbis(azanediyl)]dibenzoic acid and 5,5 '-[biphenyl-4,4 '-diylbis(azanediyl)]diisophthalic acid (H(2)L1 and H(4)L2, respectively), with different transition metals (Zn(ii), Zr(iv) and Cd(ii)) under solvothermal conditions. The reaction between H(2)L1 and Zn(NO3)(2)center dot 6H(2)O led to two different coordination networks. In PUMflex1-Zn, which has the formula [Zn4O(L1)(3)(DMF)(2)](DMF)(5)(n)center dot(DMF)(x), the ligand always displays a syn conformation (with respect to the central biphenylene scaffold), whereas in the polymorph PUMflex1.1-Zn, one of the three ligands composing the asymmetric unit adopts an anti conformation. Although the two supramolecular isomers have equivalent stoichiometry and dimensionality, they show different topologies and entanglement types: parallel polycatenation of the 6(3)-hcb and 2-fold interpenetration of the 4(4)-sql layers, respectively. In the case of PUMflex1-Zr, with the formula [Zr6O4(OH)(8)(L1)(4)(H2O)(2)](n)center dot(DMF)(x), H(2)L1 exclusively adopts the syn conformation, forming 1D-chains of rugby-ball shaped aggregates (topological type 2,8C1) interconnected through H-bonds with water molecules. In contrast, H(4)L2 behaves as a dianionic ligand in PUMflex2-Cd, with the formula [Cd(kappa(2)-COO)(2)(DMF)(3)(DMF)](n), forming 1D zig-zag chains connected through the N-HMIDLINE HORIZONTAL ELLIPSISOC(OH) H-bonds to provide planar layers of sql topology. In all cases, the ability of the amine functions to interact with the H-bond active guests is structurally highlighted by the recurrent N-HMIDLINE HORIZONTAL ELLIPSISODMF interaction modelled in the X-ray structures.
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