The influence of organic agents on the resultant crystal structure in the reactions of the [Re4Te4(CN)12]4− tetrahedral cluster anion with Nd3+ cations

The reaction of the cluster salt K4[Re4Te4(CN)12]·5H2O with NdCl3·6H2O was studied in either an acidic medium (HCl) or in a water solution in the presence of the following organic agents: hexafluoroacetylacetonate, 2,2′-bipyridine or 1,10-phenanthroline (phen). The crystal structures of four new compounds have been solved by single crystal X-ray diffraction analysis: (H)[{Nd(H2O)5}{Re4Te4(CN)12}]·5.5H2O (1) (space group P21/c, framework structure), K2[{Nd(H2O)7}2{Re4Te4(CN)12}2]·8H2O (2) (space group С2/c, isolated structure), K0.5H0.5[{Nd(H2O)5}{Re4Te4(CN)12}]·3H2O (3) (space group Сmcm, layered structure) and (phenH)[{Nd(H2O)2(phen)2}{Re4Te4(CN)12}]·11H2O (4) (space group С2/c, chain structure). 1,10-Phenanthroline was found to have been incorporated into the structure of compound 4, whilst hexafluoroacetylacetonate and 2,2′-bipyridine did not enter the structures of 2 and 3. It was shown that the structures of compounds 2–4 differ dramatically from that found for compound 1, which was obtained in the absence of the organic agents.

Four different cluster complexes based on Nd3+ cations and the tetrahedral cluster anions [Re4Te4(CN)12]4− have been synthesized and investigated. The influence of the presence of an organic agent in the mother liqueur on the resultant compounds’ structures was established by introduction of three different organic reactants that are able to coordinate metal cations by the bidentate mode.Figure optionsDownload as PowerPoint slideHighlights
► Study of the system Ln3+/polydentate ligand/[Re4Q4(CN)12]4− (Q = S, Se, and Te).
► Influence of organic agents on the resultant crystal structure.
► A new compound with large channels and with a potential solvent area corresponding to 32.0% of the unit cell volume.