Inorganic Chemistry, Vol.42, No.23, 7396-7402, 2003
Hydrothermal syntheses, crystal structures, and magnetic properties of inorganic-organic hybrid vanadium selenites with zero- to three-dimensional structures: (1,10-phenanthroline)(2)V2SeO7, (2,2'-bipyridine)VSeO4, (4,4'-bipyridine)V2Se2O8, and (4,4'-bipyridine)(2)V4Se3O15 center dot H2O
A family of inorganic-organic hybrid vanadium selenites with zero-, one-, two-, and three-dimensional structures, (1,10-phen)(2)V2SeO7, (2,2'-bipy)VSeO4, (4,4'-bipy)V2Se2O8, and (4,4'-bipy)(2)V4Se3O15-H2O (where phen = phenanthroline and bipy = bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Different bidentate organodiamine ligands and reactant concentrations were used in the four reaction systems, which are responsible for the variety of structural dimensions of the compounds. (1,10-phen)(2)V2SeO7 crystallizes in a monoclinic system with space group P211n and cell parameters a = 8.6509(3) Angstrom, b = 7.8379(2) Angstrom, c = 34.0998(13) Angstrom, beta= 91.503(2)degrees, and Z = 4. (2,2'-bipy)VSeO4 crystallizes in a monoclinic system with space group C2/c and cell parameters a = 17.0895(12) Angstrom, b = 14.7707(10) Angstrom, c = 11.7657(8) Angstrom, beta= 131.354(3)degrees, and Z = 8. (4,4'-bipy)V2Se2O8 crystallizes in a triclinic system with space group P (1) over bar and cell parameters a = 7.1810(10) Angstrom, b = 10.8937(13) Angstrom, c = 11.1811(15) Angstrom, alpha = 115.455(3)degrees, beta = 107.582(3)degrees, gamma = 91.957(4)degrees, and Z = 2. (4,4'-biPY)(2)V4Se3O15.H2O crystallizes in a monoclinic system with space group Pc and cell parameters a = 7.9889(9) Angstrom, b = 7.8448 Angstrom, c = 23.048(3) Angstrom, = 99.389(4)degrees, and Z = 2. (1,10-phen)(2)V2SeO7 has an isolated structure, (2,2'-bipy)VSeO4 has a chain structure, (4,4'-biPY)V2Se2O8 has a layered structure, and (4,4'-bipy)(2)V4Se3O15.H2O has a framework structure. The chains are constructed from VO4N2 octahedra and SeO3 pyramids, laced by organic ligands (2,2'-bipy). The layers consist of vanadium selenite chains [(VO)(2)(SeO3)(2)](infinity), linked by 4,4'-bipy molecules. The framework is composed of vanadium selenite sheets [V4Se3O16](infinity), pillared by 4,4'-bipy molecules. All of the compounds are thermally stable to 300 degreesC, and the magnetic susceptibilities confirm the existence of tetravalent V atoms in the antiferromagnetic (4,4'-bipy)V2Se2O8 complex and mixed tetravalent and pentavalent V atoms in the paramagnetic complex (4,4'-biPY)(2)V4Se3O15-H2O.