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

Abstract

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\bar{\mathrm{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)].

Graphical abstract

Keywords

ditopic ligand / substituted acetylacetone / desolvation / diffraction

RIGHTS & PERMISSIONS

Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature