An Unusual Binodal (4,12)-Connected 3D Supramolecular Network Based on [Mn4(OH)2(H2O)2]6+ Subunits

A new two-dimensional MnⅡ metal-organic framework (MOF), [Mn4(μ3-OH)2L2 (4,4 -bipy)2(H2O)2]·H2O(1, H3 L= 5-oxyacetateisophthalic acid, 4,4 -bipy = 4,4 -bipyridine) has been synthesized by the hydrothermal reaction. Complex 1 crystallizes in the monoclinic system, space group P21 /n with a = 10.420(1), b = 19.485(1), c = 11.079(1) , β = 109.63(1)°, V = 2118.8(1) 3 , C40H34 Mn4N4O19 , Mr = 1094.47, Dc = 1.715, Z = 2, F(000) = 1108, μ = 1.251, R = 0.0300 and wR = 0.0812 for 4236 observed reflections (I > 2σ(I)). Single-crystal X-ray structure analysis reveals that 1 features a two-dimensional (3,6)-connected layer constructed by [Mn4(OH)2(H2O)2]6+ clusters. The adjacent layers are further linked with each other by hydrogen bonds to produce an unusual binodal (4,12)-connected 3D supramolecular network with 4-connected L3- ligands and 12-connected tetranuclear [Mn4(OH)2(H2O)2]6+ subunits.