The synthesis and crystal structure of vanadium complexes:: [VIVO2(phen)2]•6H2O and [2,2′-(bipy)2VVO2](H2BO3)•3H2O

The organic-inorganic hybrid materials vanadium oxide [(VO2)-O-IV(phen)(2)](.)6H(2)O (1) and [(2,2'-bipy)(2)(VO2)-O-V](H2BO3)(.)3H(2)O (2) have been conventional and hydrothermal synthesized and characterized by single crystal X-ray diffraction, elemental analyses, respectively. Although the method and the ligand had been used in the syntheses of the compounds (1) and (2) are different, they almost possess similar structure. They all exhibit the distorted octahedral [VO2N4] unit with organonitrogen donors of the phen and 2,2'-bipy ligands, respectively, which coordinated directly to the vanadium oxide framework. And they are both non-mixed-valence complexes. But the compound (1) is isolated, and the compound (2) consists of a cation of [(2,2'-bipy)(2)(VO2)-O-V](+) and an anion of (H2BO3)(-). So the valence of vanadium of (1) and (2) are tetravalence and pentavalence, respectively. Meanwhile it is noteworthy that pi-pi stacking interaction between adjacent phen and 2,2'-bipy groups in compounds I and 2 also play a significant role in stabilization of the structure. Thus, the structure Of [(VO2)-O-IV(phen)(2)](.)6H(2)O and [(2,2'-bipy)(2)(VO2)-O-V](H2BO3)(.)3H(2)O are both further extended into interesting three-dimensional supramolecular. Crystal data: (1) Triclinic, P $(1) over bar $, a = 8.481(4), b = 12.097(5), and c = 14.607(6) Angstrom, alpha = 66.32(2), beta = 82.97(3), and gamma = 82.59(4)degrees, V = 1357.0(10) Angstrom(3), Z = 2, R-1 = 0.0685, wR(2) = 0.1522. (2) Triclinic, P $(1) over bar $, a = 6.643(13), b = 11.794(2), and c = 14.822(3) Angstrom, alpha = 101.39(3), beta = 101.59(3), and gamma = 97.15(3)degrees, V = 1098.8(4) Angstrom(3), Z = 2, R-1 = 0.0736, wR(2) = 0.1998. C) 2003 Elsevier Science B.V. All rights reserved.