Structural Diversity of Metal–Organic Materials Containing Bismuth(III) and Pyridine-2,5-Dicarboxylate

Three new metal–organic materials containing bismuth and pyridine-2,5-dicarboxylate (pydc) have been synthesized by hydro- and solvothermal methods and have been characterized by single crystal X-ray diffraction. Compound 1, Bi(pydc)(Hpydc)(H 2 O), crystallizes in the space group P 2 1 / c ( a = 15.4528(10) Å, b = 7.8242(5) Å, c = 12.7421(8) Å, β = 109.463(1)°) and consists of one-dimensional (1D) chains that assemble into a three-dimensional (3D) supramolecular structure via hydrogen bonding in the x -and y -directions. An interesting complex anionic layer structure containing K + ions and water molecules in the interlayer regions is observed for compound 2, K 4 Bi(pydc) 3 (Hpydc)(H 2 O) 3.3, which crystallizes in the space group P 1̅ ( a = 9.2359(5) Å, b = 9.5854(5) Å, c = 20.1439(10) Å, α = 86.062(1)°, β = 87.645(1)°, γ = 87.729(1)°). This appears to be the first example of a layered anionic bismuth metal–organic structure where the anionic slabs are separated by positively charged counterions in the interlayer region. Compound 3, (DMA + ) 3 Bi(pydc) 2 (Hpydc) 2 (DMA + = dimethyl ammonium cation), space group P 1̅ ( a = 9.6953(6) Å, b = 11.7437(7) Å, c = 18.0006(11) Å, α = 73.282(1)°, β = 78.913(1)°, γ = 78.072(1)°), has a 1D supramolecular chain structure that extends along the x -direction that also contains four-connected nodes of anionic bismuth building block similar to compound 2 . The photoluminescent properties of compound 1 are discussed.