Multivalent hydrogen‐bonded architectures directed by self‐complementarity between [Cu(2,2′‐biimidazole)] and malonate building blocks

• Published in: Acta crystallographica. Section C, Crystal structure communications Crystal structure communications, 2024-09, Vol.80 (9), p.487-496
• Main Authors: Atencio, Reinaldo, Linares, Marciel M., González, Teresa, Briceño, Alexander
• Format: Article
• Language: English
• Subjects: 2,2′‐biimidazole; Anions; Assemblies; Carboxylic acids; Chemical bonds; Chemical synthesis; Coordination compounds; Copper; copper(II); crystal structure; Helices; Hydrogen; hydrogen bonding; malonate; Metal complexes; Molecular interactions; Self-assembly; Structural analysis; supramolecular
• ISSN: 2053-2296; 0108-2701; 2053-2296; 1600-5759
• DOI: 10.1107/S2053229624007897

The synthesis and structural characterization of four novel supramolecular hydrogen‐bonded arrangements based on self‐assembly from molecular `[Cu(2,2′‐biimidazole)]' modules and malonate anions are presented, namely, tetrakis(2,2′‐biimidazole)di‐μ‐chlorido‐dimalonatotricopper(II) pentahydrate, [Cu3(C3H2O4)2Cl2(C6H6N4)4]·5H2O or [Cu(H2biim)2(μ‐Cl)Cu0.5(mal)]2·5H2O, aqua(2,2′‐biimidazole)malonatocopper(II) dihydrate, [Cu(C3H2O4)(C6H6N4)(H2O)]·2H2O or [Cu(H2biim)(mal)(H2O)]·2H2O, bis[aquabis(2,2′‐biimidazole)copper(II)] dimalonatodiperchloratocopper(II) 2.2‐hydrate, [Cu(C6H6N4)2(H2O)]2[Cu(C3H2O4)(ClO4)2]·2.2H2O or [Cu(H2biim)2(H2O)]2[Cu(mal)2(ClO4)2]·2.2H2O, and bis(2,2′‐biimidazole)copper(II) bis[bis(2,2′‐biimidazole)(2‐carboxyacetato)malonatocopper(II)] tridecahydrate, [Cu(C6H6N4)2][Cu(C3H2O4)(C3H3O4)(C6H6N4)2]·13H2O or [Cu(H2biim)2][Cu(H2biim)2(Hmal)(mal)]2·13H2O. These assemblies are characterized by self‐complementary donor–acceptor molecular interactions, demonstrating a recurrent and distinctive pattern of hydrogen‐bonding preferences among the carboxylate, carboxylic acid and N—H groups of the coordinated 2,2′‐biimidazole and malonate ligands. Additionally, coordination of the carboxylate group with the metallic centre helps sustain remarkable supramolecular assemblies, such as layers, helices, double helix columns or 3D channeled architectures, including mixed‐metal complexes, into a single structure. This study unveils the intricate crystal structures and diverse supramolecular architectures of four novel CuII complexes with 2,2′‐biimidazole and malonate ligands, showcasing their unique hydrogen‐bonded networks and their potential for use in materials science applications.