Multiple component ionic complex [CoIII(NH3)6][CoII(H2O)4(3,5-Py(COO)2)2]Cl•3H2O with partial in situ reduction of cobalt(III)
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FONARI, Marina, DARII, Mariana, BACA, Svetlana, KRAVTSOV, Victor. Multiple component ionic complex [CoIII(NH3)6][CoII(H2O)4(3,5-Py(COO)2)2]Cl•3H2O with partial in situ reduction of cobalt(III). In: Achievements and perspectives of modern chemistry, 9-11 octombrie 2019, Chişinău. Chisinau, Republic of Moldova: Tipografia Academiei de Ştiinţe a Moldovei, 2019, p. 99. ISBN 978-9975-62-428-2.
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Achievements and perspectives of modern chemistry 2019
Conferința "International Conference "Achievements and perspectives of modern chemistry""
Chişinău, Moldova, 9-11 octombrie 2019

Multiple component ionic complex [CoIII(NH3)6][CoII(H2O)4(3,5-Py(COO)2)2]Cl•3H2O with partial in situ reduction of cobalt(III)


Pag. 99-99

Fonari Marina, Darii Mariana, Baca Svetlana, Kravtsov Victor
 
Institute of Applied Physics
 
Disponibil în IBN: 5 noiembrie 2019


Rezumat

Cobalt coordination complexes that exhibit impressing redox and magnetic properties find a significant range of applications in biology and medicine [1]. Among them, hexammine cobalt(III) chloride, [Co(NH3)6]Cl3 ("Cohex"), a textbook example of a classical Werner complex with six ammonia ligands arranged in an octahedral geometry about the Co(III) ion, stands ahead [2,3]. Known for over a century, it is widely studied nowadays due to the antimicrobial and inhibition properties and if so the family of its inclusion solids based on hydrogen bonds as second sphere interactions grows extensively [4]. The cocrystalization of hexammine cobalt(III) chloride and 3,5-pyridine-dicarboxylic acid (3,5-Py(COOH)2), accompanied by the partial reduction in situ of Co(III) to Co(II), resulted in the mixed-valence Co(III,II) coordination compound [CoIII(NH3)6][CoII(H2O)4(3,5Py(COO)2)2]Cl•3H2O. Ionic complex crystallizes in the centrosymmetric triclinic space group P-1, a=7.4396(15), b=8.3675(19), c=24.286(3) Å, a=87.060(15), b=83.102(15), y=66.39(2)°, V=1375.2(5) Å3 and comprises octahedral [CoIII(NH3)6]3+ cations, two types of anions, chloride and [CoII(H2O)4(3,5-Py(COO)2)2]2-, and lattice water molecules. The Co(III)-N distances in the cation are in the range 1.93(1)-1.98(1) Å, while Co(II)-N distances in the anions are 2.14(2) and 2.11(1) Å, undoubtedly indicating the mixed-valence compound. In the Co(II) octahedral complex anion four coordinated water molecules occupy equatorial plane, while dicarboxylate residues coordinate in monodentate mode via pyridine atom in two apical positions. The crystal structure can be described as a two-dimensional array of Co(III) centers linked in the layers via hydrogen bonds with chloride anions and water molecules and alternate along the crystallographic c axis with the anionic layers built of the identical Co(II) complex anions interlinked via anionanion OH(water)…O(COO) hydrogen bonds and stacking interactions of the pyridine rings.