Abstract: | Starting from the tripodal tetradentate ligands ‐(3,5‐dibromo‐2‐hydroxybenzyl)(2‐hydroxybenzyl)(2‐pyridyl)methylamine (H2L1), (3,5‐dibromo‐2‐hydroxybenzyl)(2‐hydroxy‐5‐nitrobenzyl)(2‐pyridyl)methylamine (H2L2), and (3,5‐dichloro2‐hydroxybenzyl)(2‐hydroxy‐5‐nitrobenzyl)(2‐pyridyl)methylamine (H2L3) the new isostructural dinuclear zinc compounds [Zn2(L1)2]·N(CH2CH3)3 ( 1 ), [Zn2(L2)2]·2CH3OH ( 2 ) and [Zn2(L3)2]·C4H10O ( 3 ) were synthesized. Due to their enzyme‐like trigonal bipyramidal N2O3 coordination environment of the zinc ions and the similar Zn···Zn distances the complexes can be considered to be structural models for the active sites in phospholipase C and nuclease P1. With H2L3 also the dinuclear complex [Co2(L2)2(CH3OH)]·2CH3OH·0.5C4H10O ( 4 ) could be prepared. The new compounds were isolated and characterized by single crystal X‐ray crystallography as well as infrared spectroscopy. The cobalt compound 4 was additionally characterized by UV‐Vis spectroscopy and magnetic measurements. 1 crystallizes in the monoclinic space group P21/n with a = 11.2814(2), b = 28.6154(2), c = 13.1866(3) Å, β = 96.995(1)°, V = 4225.2(2) Å3, Z = 4. 2 and 3 are monoclinic, space group C2/c with a = 23.084(5), b = 9.232(2), c = 21.849(4) Å, &β; = 96.83(3)°, V = 4623(2) Å3, Z = 4, and a = 22.7834(3), b = 9.2463(1), c = 21.6351(3) Å, &β; = 97.592(1)°, V = 4517.7(2) Å3, Z = 4, respectively. 4 crystallizes in the monoclinic space group I2/a with a = 22.4680(4), b = 20.5517(4), c = 22.8910(6) Å, &β; = 111.938(1)°, V = 9804.7(4) Å3, Z = 8. 4 shows an effective magnetic moment of 6.72 μB at 300 K which clearly indicates the presence of two cobalt(II) high spin ions with Curie‐Weiss behaviour above 80 K. At lower temperatures a decrease of the effective magnetic moment was observed. |