Hydrothermal synthesis and characterization of a new 3D vanadium(III) phosphite (CHNH)(CHNH)[V(HPO)(HO)]1.5HO

A new vanadium(III) phosphite, (C4H8N2H4)0.5(C4H8N2H3)[V4(HPO3)7(H2O)3]1.5H2O, has been synthesized hydrothermally by using V2O5, H3PO3 as reactants, piperazine as the structure-directing agent. The as-synthesized product was characterized by powder X-ray diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis, and SQUID magnetometer. Single-crystal X-ray diffraction analysis shows that the title compound crystallized in the trigonal space group P3¯c1 (No. 165) with the parameters: a=13.4678(4)Å, c=18.3171(8)Å, V=2877.27(17)Å3 and Z=4. Its structure is built up by alternation of octahedral VO6 or VO5(H2O) and pseudo-pyramidal HPO3 units to form infinite 2D layers, and these layers are interconnected by sharing vertex-oxygen with octahedral VO6 units to generate a 3D open-framework structure with 12-membered ring channels in a and b directions, respectively, where there exist entrapped diprotonated and mono-protonated piperazine cations, and water molecules. Magnetic measurement indicates that paramagnetic behavior is observed down to 4K.