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

Abstract Two new heteropoly tungstovanadate derivatives, [Fe(phen) 3 ] 2 [W 10.5 V 4.5 O 42 ]·3H 2 O (1) and [Fe(phen) 3 ] 2 [W 10 V 5 O 42 ].6H 2 O (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 72 H 54 Fe 2 N 12 O 45 V 4.5 W 10.5 , monoclinic, space group C2/c , a = 30.244 ( 9 ) A , b = 13.586 ( 3 ) A , c = 24.707 A , β = 99.882 (8)°, V = 10002 (5) A 3 , Z = 4 ; for compound 2, C 72 H 60 Fe 2 N 12 O 48 V 5 W 10 , monoclinic, space group C2/c , a = 30.246 (6) A, b = 13.909 ( 3 ) A , c = 25.329 (5) A, β = 100.34 (3)°, V = 10483 (4) A 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.