Exploiting the Pyrazole-Carboxylate Mixed Ligand System in the Crystal Engineering of Coordination Polymers

The utility of the pyrazole-carboxylate mixed ligand system has been probed with the synthesis of five new coordination polymers, derived from bis-pyrazole ligand 4,4′-methylenebis­(3,5-dimethyl-1H-pyrazole) H2L1, large semirigid dicarboxylate coligands, and the deliberately designed and synthesized ligand para-((3,5-dimethyl-1H-pyrazol-4-yl)­methylene)­benzoic acid H2L4. Complex poly-[Co­(H2L1)­(L2)­(OH2)]·1/2H2O 1 features the coligand (S,S)-1,4,5,8-naphthalenetetracarboxylic diimide-N,N′-bis­(2-propionate) L2, and comprises chiral two-dimensional sheets, associating via substantial π–π stacking interactions. Complexes 2 and 3 contain the coligand 1,4-bis­((3-carboxyphenyl)­methyl)­piperazine L3. Complex poly-[Co­(H2L1)2(L3)] 2 is a two-dimensional polymer containing octahedral Co­(II) ions, whereas modifying the synthesis conditions gave complex poly-[Co2(HL1)2(L3)] 3, a three-dimensional α-Po structure containing pyrazolate-bridged dimers of tetrahedral Co­(II) ions, displaying weak antiferromagnetic coupling. Magnetic data for complex 3 fitted well to a S = 3/2 Heisenberg (−2JS1.S2) dimer model with J = −3.2 cm–1 and g = 2.25. We then prepared the new heteroditopic ligand para-((3,5-dimethyl-1H-pyrazol-4-yl)­methylene)-benzoic acid H2L4, and the complexes poly-[Co­(HL4)2]·H2O 4 and poly-[Cu­(HL4)2]·2MeOH 5, which demonstrate for the first time the tendency of flexible pyrazole-carboxylate coordination polymers with perfectly commensurate linker dimensions to lead to low-dimensional assemblies. These results give fresh insight into the structural properties of flexible bispyrazole-carboxylic acid systems as a function of coligand dimensions, and provide new directions for designed polymeric cluster compounds.