Influence of the Arene/Perfluoroarene Ratio on the Structure and Non-Covalent Interactions in Crystals of Cd Compounds

• Published in: Crystals (Basel) 2023-04, Vol.13 (4)
• Main Authors: Voronina, Julia K, Yambulatov, Dmitriy S, Chistyakov, Aleksander S, Bolot’ko, Alena E, Efromeev, Leonid M, Shmelev, Maxim A, Sidorov, Alexey A, Eremenko, Igor L
• Format: Article
• Language: English
• ISSN: 2073-4352; 2073-4352
• DOI: 10.3390/cryst13040678

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)[sub.2](phen)][sub.n] (1), [Cd(NO[sub.3])(pfb)(phen)][sub.n] (2), [Tb[sub.2]Cd[sub.2](pfb)[sub.10](phen)[sub.2]]. 3MeCN][sub.n] (3), [Tb[sub.2]Cd[sub.2](NO[sub.3])[sub.2](pfb)[sub.8](phen)[sub.2] [sup..]1.5MeCN][sub.n] (4), [Cu[sub.2](Afb)[sub.4](phen)[sub.2]] (5), [Cu[sub.2](NO[sub.3])[sub.2](Afb)[sub.2](phen)[sub.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 NO[sub.3] [sup.−] 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.