Synthesis and crystal structure of a novel organic-inorganic hybrid hexavanadate [(phen)4V6O12(CH3OH)4]·2CH3OH·4H2O

A novel organic-inorganic hybrid vanadium oxide [(phen)4V6O12(CH3OH)4]·2CH3OH·4H2O (phen=1,10-phenanthroline) was synthesized by hydrothermal technique combined with conventional method and structurally characterized by elemental analysis, IR, UV, EPR spectra, TG analysis and single crystal X-ray diffraction. Black-brown crystals crystallized in the monoclinic system, space group P21/c, a=9.600 (6) Å, b=22.113 (14) Å, c=14.134 (9) Å, β=96.969 (10)°, V=2978 (3) Å3, Z=2, and R1(wR2)=0.0546 (0.1457). In the title compound, a non-mixed-valence hybrid hexavanadate (phen)4VIV6O12(CH3OH)4 is constructed by phen and methanol molecules coordinated directly to the vanadium oxide framework. A novel 12-membered ring with a central porous structure is built up by vanadium and bridging oxygen atoms. A one-dimensional supramolecular chain is formed by hydrogen bonding interactions between hexavanadate and solvent molecules. Two-dimensional layer is stabilized by intra-chain π⋯π stacking interaction.