The zinc(II) complexes with ortho-hydroxy substituted arylhydrazo-β-diketonates [Zn2(CH3OH)2(μ-L1)2] (5), [Zn{(CH3)2SO}(H2O)(L2)] (6), [Zn2(H2O)2(μ-L3)2] (7) and [Zn(H2O)2(L4)]·H2O (8) were synthesized by reaction of a zinc(II) salt with the appropriate hydrazo-β-diketone, HO-2-C6H4-NHN
C{C(
O)CH3}2 (H2L1, 1), HO-2-O2N-4-C6H3-NHN
C{C(
O)CH3}2 (H2L2, 2), HO-2-C6H4-NHN![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CC(
O)CH2C(CH3)2CH2C
(
O) (H2L3, 3) or HO-2-O2N-4-C6H3-NHN![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CC(
O)CH2C(CH3)2CH2C
(
O) (H2L4, 4). They were fully characterized, namely by X-ray diffraction analysis that disclosed the formation of extensive H-bonds leading to 1D chains (5 and 6), 2D layers (7) or 3D networks (8). The thermodynamic parameters of the Zn(II) reaction with H2L2 in solution, as well as of the thermal decomposition of 1–8 were determined. Complexes 5–8 act as diastereoselective catalysts for the nitroaldol (Henry) reaction. The threo/erythro diastereoselectivity of the β-nitroalkanol products ranges from 8 : 1 to 1 : 10 with typical yields of 80–99%, depending on the catalyst and substrate used.
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