Two types of coordination polymers based on cluster anions [Re4Q4(CN)12]4− (Q = S, Se) and cations of rare-earth metals Ln3+: Syntheses and crystal structures

The reactions of aqueous solutions of the tetrahedral cluster anions [Re4Q4(CN)12]4− (Q = S, Se) with lanthanide chlorides resulted in the crystallization of the formed compounds into two main structural types [{Ln(H2O)4(H2O)2/3Cl1/3}3{Re4Q4(CN)12}2]·2H2O (Ln = La–Gd, Q = S, Se) and K0.5(H)0.5[{Ln(H2O)4}{Re4S4(CN)12}]·nH2O or (H)[{Ln(H2O)4}{Re4Se4(CN)12}]·nH2O (Ln = Tb–Lu). Compounds of the first type crystallize in the hexagonal crystal system (space group Р63/m) and they have a three-dimensional polymeric structure; compounds of the second type crystallize in the orthorhombic crystal system (space group Cmcm) and they have a two-dimensional crystal structure due to the polymeric anion {[{Ln(H2O)4}{Re4Q4(CN)12}]−}∞∞.

Graphical abstractTwo series of cyano-bridged cluster complexes based on the cluster anions [Re4S4(CN)12]4− and [Re4Se4(CN)12]4− and lanthanide group cations have been synthesized and structurally characterized. They are crystallized into two main structural types. Compounds of the first type crystallize in the hexagonal crystal system (space group Р63/m) and they have a three-dimensional polymeric structure; compounds of the second type crystallize in the orthorhombic crystal system (space group Cmcm) and they have a two-dimensional crystal structure.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► [Re4Q4(CN)12]4− as building blocks for the construction of coordination polymers. ► 25 new complexes based on cluster anions [Re4Q4(CN)12]4− and lanthanide cations are described. ► Two structural types are found in the system Ln(lanthanide)/[Re4Q4(CN)12]4− (Q = S, Se).