Interplay of Isomorphs and Polymorphs of Amidino-Copper(II) Complexes with Different Halides

• Published in: Crystals (Basel) Vol. 14; no. 4; p. 319
• Main Authors: Yamba, Zaina, Peoble, Anna, Novikov, Egor, Castañeda, Raúl, Timofeeva, Tatiana
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 01.04.2024
• Subjects: Atomic structure; Chloride; Contrast agents; Copper; Copper bromide; Copper chloride; Copper compounds; Cu(II) complexes; Decomposition; Diffraction; Dimers; EPR; Ethanol; Gadolinium; Halides; Infrared spectroscopy; isomorphs; Ligands; Magnetic resonance imaging; polymorphs; Pressure vessels; Pyrazole; Pyridine; Pyridines; Pyrimidines; Quantum chemistry; Sodium bromides; Spectrum analysis; Synthesis; Thermal stability; Toxicity; X-rays
• ISSN: 2073-4352; 2073-4352
• DOI: 10.3390/cryst14040319

To increase the number of potential materials for application as MRI contrast agents, several Cu(II) complexes were synthesized. Cu(II) complexes were chosen because they are less expensive in comparison with the presently used Gd(III), Mn(II) and other agents. Pyridine-2-carboximidamide (1), pyrimidine-2-carboximidamide (2) and pyrazole-2-carboximidamide (3) in the form of different salts along with CuCl2 and NaCl or CuBr2 and NaBr were used to obtain four Cu(II) complexes: dichloro-pyrimidine-2-carboximidamide copper(II) (4), dibromo-pyrimidine-2-carboximidamide copper(II) (5), dichloro-pirazole-2-carboximidamide copper(II) (6), and dibromo-pirazole-2-carboximidamide copper(II) (7). X-ray diffraction analysis revealed that molecular complexes 4–7 contain square planar coordinated Cu(II) atoms and their structures are very similar, as well as their packing in crystals, which allows us to consider them isomorphs. The same synthetic approach to complex preparation where NaCl or NaBr was not used brought us to the formation of dimeric complexes μ-chloro{chloro(pyridine-2-carboximidamide)copper(II)} (8) and μ-chloro{chloro(pyrimidine-2-carboximidamide)copper(II)} (9). In the dimeric complexes, two fragments which were the same as in monomeric complexes 4–7 are held together by bridging Cu-Cl bonds making the coordination of Cu equal to 5 (square pyramid). In dimeric complexes, axial Cu-Cl bonds are 2.7360 and 2.854 Å. These values are Cu-Cl bonds on the edge of existence according to statistical data from CSD. Synthesized complexes were characterized by IR spectroscopy, TGA, PXRD, EPR, and quantum chemical calculations. The higher thermal stability of monomer pyrimidine-based complexes with Cl and Br substituents makes them more prospective for further studies.