Discrete versus 1D Compounds based on Pentagonal Bipyramid Coordination Geometries: A Matter of Solubility?

A series of heterometallic compounds based on the association of trans‐dicyanido Cr(III) complex [Cr(L)(CN)2]K ⋅ 2H2O and several divalent [MnII(H2Ln)Cl2] heptacoordinated complexes, where Ln stands for pentadentate ligands featuring a planar N3O2 coordination pocket and various substituents (NH2, cyclohexyl, S,S‐mandelic), is described. A dinuclear compound [Cr(L)(CN)2M(H2L2)] and 1D coordination polymers of general formula [Cr(L)(CN)2M(H2Ln)]X (X=PF6− or [Cr(L)(CN)2]−) were rationally prepared by a simple adjustment of the Cr : M stoichiometry for R=NH2 or tuning the solvent mixtures to promote the crystallization of discrete complexes or chains. The crystal structures, phase purities and magnetic properties of all the compounds are reported. A series of heterometallic compounds based on the association of heptacoordinated trans‐dicyanido Cr(III) complex [Cr(L)(CN)2]K and divalent [MnII(H2Ln)Cl2] complexes incorporating pentadentate ligands with a planar N3O2 coordination pocket and various R substituents illustrate the subtle effect of R on the selective crystallization of discrete or 1‐D heterometallic cyanido‐bridged compounds.