A Covalent Vanadium(III) 2-Dimensional Network and Vanadyl Chains Linked by Aryldioxides

Thermolysis of (iPrO)4V and 2,6-dihydroxynaphthalene in 4-(3-phenylpropyl)pyridine afforded [mer-V(μ2,6-OC10H6O)1.5(4-(3-phenylpropyl)py)3] n (1; C57H54N3O3V, triclinic, P1̄, a = 10.450(2) Å, b = 14.098(3) Å, c = 16.765(3) Å, α = 100.09(3)°, β = 103.85(3)°, γ = 103.08(3)°, Z = 2) and oxidation product bis-2,6-dinaphthol. Paramagnetic (S = 1) 1 adopts a bricklike motif of aryldioxide-connected V(III) centers whose channels are filled with the bound 4-(3-phenylpropyl)py. A similar procedure involving (iPrO)3VO provided the linear chain [(μ2,6-OC10H6O)(4-(3-phenylpropyl)py)2VO] n (2; C38H36N2O3V, monoclinic, P21/c, a = 10.6172(2) Å, b = 9.4477(3) Å, c = 31.8129(8) Å, β = 95.20(3)°, Z = 4). Interchain pyridine ring-edge to phenyl-face interactions generate a sheet of like-oriented oxos, but adjacent sheets are oriented in opposition so that no net dipole exists. Another 1-dimensional chain, [(μ1,4-OC6H4O)(py)2VO] n (3; C16H14N2O3V, monoclinic, P21/c, a = 8.377(2) Å, b = 16.675(3) Å, c = 11.061(2) Å, β = 103.91(3)°, Z = 4), was prepared by heating (iPrO)4V and hydroquinone in pyridine. Pyridines of adjacent chains interpenetrate to form a sheet, but oxos in adjacent chains are now in opposition.