Hydrolysis of 4-nitrophenyl acetate by a mu(2)-OH-bridged zinc complex: Crystal structure of [Zn(oapy)(OAc)(mu(2)-OH)] and [ZnL(mu(2)-SO4)](4)center dot 6H(2)O (oapy is 2-aminopyridine and L is 2,5,8-triaza-1,9-di(2-fluorozenzyl)nonane)

摘要

Two new complexes, [Zn(oapy)(OAc)(mu(2)-OH)] (1) and [ZnL(mu(2)-SO4)](4)(.)6H(2)O (2), were prepared and structurally characterized, where oapy is o-aminopyridine, OAc is acetate, and L is 2,5,8-triaza-1,9-di(2-fluorozenzyl)nonane. The X-ray structure analysis reveals that I crystallizes in the monoclinic system with space group P2(1)/c, with a = 8.849(9), b = 5.391(5), c = 19.733(19) Angstrom, beta = 98.467(13)degrees, V = 931.2(16) Angstrom(3), and Z = 4.1 is a mu(2)-OH bridged ID chain complex along b. The Zn2+ ion is four-coordinated by one N atom from an oapy, and three O atoms from two hydroxyl groups and an acetate ion, leading to a distorted tetrahedral geometry of Zn2+. 2 crystallizes in space group PT with a = 15.86(3), b = 17.05(3), c = 19.85(4) Angstrom, alpha = 74.60(4), beta = 66.93(3), gamma = 65.33(4)degrees, V = 4456(16) Angstrom(3), and Z = 2. Compound 2 is a 1D chain-like complex linked by mu(2)-(O,O')-SO4 bridges. Each simplest unit of the complex is a tetranuclear zinc(II) unit. In each unit the four non-equivalent zinc atoms, are similarly five-coordinated by three N atoms from L and two 0 atoms from two sulfate bridges. The coordination geometry of two zinc atoms is trigonal bipyramidal, the other two are in square pyramidal coordination. 1 has obvious catalytic activity to hydrolysis of 4-nitrobenyl acetate, but 2 does not.