Syntheses and Crystal Structures of Two Cobalt Carboxylate−Phosphonates with 4,4′‐Bipyridine as a Secondary Metal Linker

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The hydrothermal syntheses and crystal structures of two novel cobalt carboxylate−phosphonates with 4,4′‐bipyridine (4,4′‐bipy) as the secondary metal linker are reported. Compound 1, [Co3(H2L)2(H2O)4(4,4′‐bipy)], where H5L = 4‐HO2CC6H4CH2N(CH2PO3H2)2, crystallizes in the monoclinic space group C2/c with a = 25.9281(5), b = 9.76310(10), c = 17.3671(5) Å, β = 103.290(2)°, V = 4278.6(2) Å3, and Z = 4. Its structure contains a pillar‐layered architecture in which CoII octahedra are linked by carboxylate−phosphonate ligands to form a 2D layer and these layers are crosslinked further by 4,4′‐bipy ligands to form a porous 3D network. Compound 2, [Co2(PMIDA)(H2O)5(4,4′‐bipy)]·4H2O, where H4PMIDA = H2O3PCH2N(CH2CO2H)2, crystallizes in the triclinic space group P1 with a = 7.8009(7), b = 13.4560(12), c = 13.5453(12) Å, α = 65.207(2), β = 88.035(2), γ = 77.135(2)°, V = 1255.57(19) Å3, and Z = 2. The crystal structure of compound 2 contains 1D zigzag chains in which two cobalt(II) ions are bridged by PMIDA ligand to form dimeric units, and these dimeric units are connected further by bridging 4,4′‐bipy ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)