Hydrothermal synthesis and characterization of two new bicapped Keggin heteropoly tungstovanadated derivatives

Two new heteropoly tungstovanadate derivatives, [Fe(phen) 3] 2[W 10.5V 4.5O 42]·3H 2O (1) and [Fe(phen) 3] 2[W 10V 5O 42].6H 2O (2) (phen=1,10′-phenanthroline), have been synthesized under hydrothermal conditions by using different starting materials, and characterized by elemental analysis, IR, ESR, XPS, TGA and single-crystal X-ray diffraction analysis. Crystal data for compound 1: C 72H 54Fe 2N 12O 45V 4.5W 10.5, monoclinic, space group C2/c, a = 30.244 ( 9 ) Å , b = 13.586 ( 3 ) Å , c = 24.707 Å , β = 99.882 (8)°, V = 10002 (5) Å 3, Z = 4 ; for compound 2, C 72H 60Fe 2N 12O 48V 5W 10, monoclinic, space group C2/c, a = 30.246 (6) Å, b = 13.909 ( 3 ) Å , c = 25.329 (5) Å, β = 100.34 (3)°, V = 10483 (4) Å 3, Z = 4 . The crystal structure analysis reveals that both polyoxoanions are decorated with the [Fe(phen) 3] 2+ cations , and that they have analogous structure to each other with slightly different packing modes of the polyoxoanions, [Fe(phen) 3] 2+ cations and water molecules. They are further linked to form two-dimensional (2D) supramolecular networks through extensive hydrogen bonding. Two new heteropoly tungstovanadate derivatives, [Fe(phen) 3] 2[W 10.5V 4.5O 42]·3H 2O( 1) and [Fe(phen) 3] 2[W 10V 5O 42]·6H 2O( 2) (phen=1,10′-phenanthroline), have been synthesis under hydrothermal conditions by using different starting materials. Compound 1 is the first example of discrete bicapped Keggin heteropoly tungstovanadates. Polyoxoanions, [Fe(phen) 3] 2+ cations and water molecules act as building blocks to form two-dimensional (2-D) supramolecular layers through extensive hydrogen bonding.