Influence of the Arene/Perfluoroarene Ratio on the Structure and Non-Covalent Interactions in Crystals of Cd(II), Cd(II)-Tb(III) and Cu(II) Compounds

Abstract

The influence of arene/perfluoroarene ratio on the structure and crystal packing of carboxylate and nitrate-carboxylate complexes of Cd, Cd-Tb and Cu was studied, using the following compounds: pentafluorobenzoate (pfb) and 4-allyl-2,3,5,6-tetrabenzoate (Afb) anions and 1,10-phenanthroline (phen) composition [Cd(pfb)2(phen)]n (1), [Cd(NO3)(pfb)(phen)]n (2), [Tb2Cd2(pfb)10(phen)2]. 3MeCN]n (3), [Tb2Cd2(NO3)2(pfb)8(phen)2.1.5MeCN]n (4), [Cu2(Afb)4(phen)2] (5), [Cu2(NO3)2(Afb)2(phen)2] (6). It is shown that the main contribution to the stabilization of the crystal packing of coordination polymers 1–4 and molecular binuclear complexes 5 and 6 can be attributed to non-covalent π···π, C-H···F, and C-F···π interactions. It was found that the partial exchange of pfb or Afb anions on compact NO3− anions leads to a decrease in steric hindrance, a more efficient overlap of aromatic fragments, and a significant change in the geometry of complexes. Synthesized compounds were characterized by X-ray diffraction analysis, IR spectroscopy, and CHN analysis. The thermal stability of complexes 1 and 2 was studied. Non-covalent interactions were analyzed using the Hirshfeld surface method.

Keywords

• complexes of cadmium
• terbium and copper(II)
• pentafluorobenzoates
• 4-Allyl-2,3,5,6-tetrafluorobenzoates
• directed synthesis
• non-covalent interactions