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Interplay of Isomorphs and Polymorphs of Amidino-Copper(II) Complexes with Different Halides
Zaina Yamba ; Anna Peoble ; Egor M. Novikov , et al. Crystals,2024,14(4):319. DOI: 10.3390/cryst14040319
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Abstract: 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 ?. 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.
Keywords: isomorphs ; polymorphs ; Cu(II) complexes ; EPR
Purchased from AmBeed: 51285-26-8
CAS No. : | 51285-26-8 | MDL No. : | MFCD00052271 |
Formula : | C6H8ClN3 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | GMHCEDDZKAYPLB-UHFFFAOYSA-N |
M.W : | 157.60 | Pubchem ID : | 12403615 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; sodium hydroxide; bromine; potassium carbonate; In chloroform; | Referential Example 1 2-(2-Pyridyl)-1,4,5,6-tetrahydro-6-(4-methylbenzenesulfonyl)imidazo[4,5-d][ 1]benzazepine In 30 mL of chloroform was dissolved 2.0 g of <strong>[24310-36-9]1,2,3,4-tetrahydro-1-(4-methylbenzenesulfonyl)-1-benzazepin-5-one</strong>, to which was then added dropwise a solution of 0.33 mL of bromine in 10 mL of chloroform. The mixture was stirred at room temperature for one hour. The reaction mixture was rinsed with saturated sodium hydrogencarbonate and then dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was dissolved in 30 mL of chloroform. To the solution were added 5.0 g of 2-amidinopyridinium hydrochloride hydrate and 5.3 g of potassium carbonate, and the mixture was refluxed upon heating for 10 hours. The reaction mixture was cooled, and the solvent was then distilled off. To the resulting residue was added 30 mL of a 1M hydrochloric acid aqueous solution, and a deposited solid was collected by filtration. The resulting solid was suspended in chloroform and rinsed with a 1M sodium hydroxide aqueous solution, and the chloroform layer was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was recrystallized from ethanol to obtain 1.70 g of the titled compound. 1H-NMR (DMSO-d6): delta2.12 (3H, s), 3.00 to 3.33 (4H, br), 7.13 (2H, d, J=8.1 Hz), 7.21 (1H, dt, J=1.4 Hz, 8.1 Hz), 7.29 to 7.43 (5H, m), 7.89 (1H, dt, J=1.4 Hz, 8.1 Hz), 8.07 (1H, d, J=8.1 Hz), 8.17 (1H, d, J=7.3 Hz), 8.60 (1H, d, J=4.4 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | A mixture of 157.8 g. (1.0 mol) of 2-pyridinecarboxamidine hydrochloride 23, 54.2 g (1.0 mol) of sodium methoxide in 400 ml of dry methanol was stirred for 30 minutes. The sodium chloride was filtered and the filtrate was concentrated to dryness. The residue and 83 g (1.0 mole) of 3-methoxyacrylonitrile 24 were heated (100-160°) together for 3 hours, at this point the evolution of ethanol had stopped and the melt had started to crystallize. The product 25 was cooled to room temperature, suspended in methanol, filtered and dried to obtain 25 125.6 g, (73percent yield). |
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