Crystal-to-crystal transformation from the triclinic to the cubic crystal system by partial desolvation

2018年第12卷第3期

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《化学科学与工程前沿（英文）》 >> 2018年第12卷第3期 doi: 10.1007/s11705-018-1743-6

Crystal-to-crystal transformation from the triclinic to the cubic crystal system by partial desolvation

Institute of Inorganic Chemistry, RWTH Aachen University, Aachen, Germany

录用日期： 2018-08-23 发布日期： 2018-09-18

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摘要

Diffusion reaction of the labile building block Mg(acacCN)₂ (acacCN= 3-cyanoacetylacetonate) with silver salts leads to a series of solvated Mg/Ag bimetallic coordination polymers with composition [Mg(acacCN)₃Ag]·solvent. Despite their common stoichiometry, the topology of these polymers depends on the solvent of crystallization. The two-dimensional coordination compound [Mg(acacCN)₃Ag]·4CHCl₃ in space group P $\overset{&OverBar;}{1}$ is obtained as platelet-shaped crystals from a mixture of methanol and chloroform. When kept in the reaction mixture, these thin plates within one week convert to isometric tetrahedral crystals of the 3D network [Mg(acacCN)₃Ag]·2CHCl₃ in the cubic space group P2₁3. The transformation reaction proceeds via dissolution and recrystallization. The co-crystallized solvent molecules play an important role for stabilizing the target structure: They subtend Cl···Cl contacts and interact via non-classical C–H···O hydrogen bonds with the coordination framework. In the new cubic coordination network, both Mg(II) and Ag(I) adopt octahedral coordination, with unprecedented face-sharing by bridging O atoms of three acetylacetonato moieties. Prolonged standing of [Mg(acacCN)₃Ag]·2CHCl₃ in the reaction medium leads to further degradation, under formation of [Ag(acacCN)].

关键词

ditopic ligand ; substituted acetylacetone ; desolvation ; diffraction