Testing the High Spin Mn^II₉W^V₆ Cluster as Building Block for Three-Dimensional Coordination Networks

Pentadecanuclear high spin cyano-bridged {M′II9M′′V6(CN)48(solv)24} (M′ = 3d metal ions; M′′ = Mo, W; solv = H2O, alcohol) clusters are considered as building blocks for three-dimensional open networks. Self-assembly of MnII9WV6 clusters (S = 39/2) with 4,4′-bipyridine leads to their organization into an organic−inorganic hybrid coordination network {MnII9(4,4′-bpy)4[WV(CN)8]6(EtOH)12(H2O)4}·10EtOH 1 (System, triclinic; space group: P1̅, a = 17.1569(2) Å, b = 17.3835(2) Å, c = 19.2530(2) Å, α = 103.5520(10)°, β = 115.3950(10)°, γ = 98.3060(10)°, Z = 1). The clusters are connected through 4,4′-bpy spacers into a two-dimensional square-grid coordination framework extended in the ab crystallographic plane with the smallest intercluster separation along the a (Mn···W = 7.12 Å) and b (Mn···W = 7.15 Å) directions significantly lower than that along the c crystallographic direction (Mn···W = 8.64 Å). Direct current magnetic measurements suggest strong dominance of intracluster antiferromagnetic MnII−WV coupling over a very weak intercluster antiferromagnetic interaction.