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Snapshot and crystallographic observations of kinetic and thermodynamic products for NO 2 S 2 macrocyclic complexes

Park, In-Hyeok ; Kang, Yunji ; Lee, Eunji ; [et al.]

International Union of Crystallography (IUCr) ; 2018

In: IUCrJ Vol. 5, No. 1 ( 2018-01-01), p. 45-53

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In: IUCrJ, International Union of Crystallography (IUCr), Vol. 5, No. 1 ( 2018-01-01), p. 45-53

Abstract: Direct observation and structural characterization of a kinetic product and a thermodynamic product for complexes with an NO 2 S 2 macrocycle ( L ) are reported. L reacts with copper(I) iodide to give a mononuclear complex [Cu( L )] 2 (Cu 2 I 4 )·2CH 2 Cl 2 ( 1 ), featuring three separate units. When cadmium(II) iodide was reacted with L , an anion-coordinated complex [Cd( L )I] 2 (Cd 2 I 6 )·4CH 3 CN ( 2 ) with a needle-type crystal shape was formed as the kinetic product. Interestingly, when the needle-type kinetic product was left undisturbed in the mother solution it gradually transformed to the pseudo-dimer complex [Cd 2 ( L ) 2 I 2 ](Cd 2 I 6 ) ( 3 ) with a brick-type crystal shape as the thermodynamic product. The dissolution–recrystallization process resulted in the elimination of the lattice solvent molecules (acetonitrile) in 2 and the contraction of two neighboring macrocyclic complex units [Cd( L )I] + , forming the pseudo-dimer 3 via an intermolecular Cd...I interaction between two monomers. For the entire process from kinetic to thermodynamic products, it was possible to obtain sequential photographic snapshots, single-crystal X-ray structures and powder X-ray diffraction patterns. For the copper(I) and cadmium(II) complexes, competitive NMR results agree with the solid-state data that show copper(I) has a higher affinity for L than does cadmium(II).

Type of Medium: Online Resource

ISSN: 2052-2525

URL: Article