Hydrothermal synthesis and structural characterization of two 1-D and 2-D Dawson-based phosphotungstates

Two new Dawson-based phosphotungstates (H2en)0.5H[Cu(en)2(H2O)]2{[Cu(en)2](α1-P2W17CuO61)}·8H2O (1) (en=ethylenediamine) and [4,4′-H2bpy]2{[Cu(4,4′-bpy)3][Cu(4,4′-bpy)4(H2O)2]2[Cu(4,4′-bpy)][α-P2W18O62]2}·6H2O (2) (4,4′-bpy=4,4′-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the triclinic space group P−1 with a=11.7626(17), b=13.246(2), c=29.350(5) Å, α=87.355(5), β=79.583(5), γ=66.993(3)°, V=4138.3(11) Å3, Z=2, GOF=1.089, R1=0.0563 and wR2=0.1505, whereas 2 belongs to the orthorhombic space group Iba2 with a=22.277(8), b=47.04(2), c=22.153(8) Å, V=23215(17) Å3, Z=4, GOF=1.051, R1=0.0627 and wR2=0.1477. 1 consists of a 1-D linear chain structure constructed from monocopperII-substituted Dawson polyoxoanions, while 2 represents the first 2-D sheet-like structure with a (4,4)-connected topological net built up from plenary Dawson-type polyoxoanions and CuII-4,4′-bpy complex cations in polyoxometalate chemistry.

Two Dawson-based phosphotungstates (H2en)0.5H[Cu(en)2(H2O)]2{[Cu(en)2](α1-P2W17CuO61)}·8H2O (1) and [4,4′-H2bpy]2{[Cu(4,4′-bpy)3][Cu(4,4′-bpy)4(H2O)2]2[Cu(4,4′-bpy)][α-P2W18O62]2}·6H2O (2) have been hydrothermally synthesized and structurally characterized. 1 consists of a 1-D linear chain structure constructed from monocopper-substituted Dawson polyoxoanions, while 2 represents the first 2-D sheet-like structure with a (4,4)-connected topological net built up from saturated Dawson-type polyoxoanions and CuII-4,4′-bpy complex cations in polyoxometalate chemistry.Figure optionsDownload as PowerPoint slide