A Series of Early Lanthanide Chloranilate Frameworks with a Square Grid Topology

A series of lanthanide chloranilate frameworks containing a (4,4)-net with LaIII, CeIII, NdIII, SmIII, and EuIII have been synthesised and structurally characterised. Two structure types of square grids were obtained for these frameworks. Type 1 consists of the formula (Et4N)[Ln(can)2(H2O)] (Ln = LaIII, CeIII, NdIII; H2can = chloranilic acid) and crystallised in the tetragonal space group I4/m, featuring a nine-coordinate lanthanide ion with a coordinated water molecule and four chloranilate ligands. Type 2, (Et4N)[Ln(can)2] (SmIII and EuIII) crystallised in the I4/mcm space group, and contains an eight-coordinate lanthanide ion without a coordinated water molecule. A single-crystal-to-single-crystal transformation was carried out for (Et4N)[Nd(can)2(H2O)] on removal of the coordinated aqua ligand.