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Abstract: The interaction of LiN(SiMe3)CH2Ph with one equivalent of benzenitrile gave the N-silyl-N′-benzyl-benzamidinato-lithium compound [{Me3SiNC(Ph)N(CH2Ph)}Li(Et2O)]2 (1). The derivative zirconium and hafnium compounds were produced by the treatment of 1 with ZrCl4 or HfCl4 in tetrahydrofuran or diethyl ether at ambient temperature, respectively, with the general formula [Me3SiNC(Ph)N(CH2Ph)]3MCl (M=Zr (2), Hf (3)). Compounds 1, 2 and 3 were also characterized by X-ray single crystal diffraction and NMR analysis. [Copyright &y& Elsevier]

Abstract: Assemblies of an angular dipyridyl ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) with a series of metal perchlorate afford five new supramolecular complexes with the general formula of [M(4-bpo)2(H2O)4]·(4-bpo)2 ·(anion)·(solvent), in which M=MnII for 1, FeII for 2, CoII for 3, ZnII for 4, and FeIII for 5. Although similar molecular structures and compositions are found for these mononuclear complexes, they display two types of supramolecular lattices. Complexes 1, 4 and 5 similarly crystallize in space group P2/n or P2/c. The complex cations, free 4-bpo and lattice water are linked to generate 2D layered frameworks with the aid of hydrogen bonding, and the counter anions are located within and between (also methanol in 5) these 2D arrays. However, complexes 2 and 3 are isostructural in space group . Two types of alternate 2D layers consisting of complex cations and free 4-bpo components, respectively, are observed with the anions and lattice water locating between them. These motifs are interlinked by complicated hydrogen-bonding to form a 3D intercalated network. Moreover, when Co(NO3)2 is used instead of Co(ClO4)2 in the assembly of 3, a 1D polymeric chain complex {[Co(4-bpo)(H2O)2(NO3)2](H2O)3} n (6) is generated. These results indicate that the choice of metal ion and anion exerts a significant influence on governing the target complexes. A comparison of the structural features for all metal perchlorate complexes with 4-bpo is also briefly discussed. [Copyright &y& Elsevier]