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A Zr complex [Zr 4 L 2 (μ 3 -O) 2 (μ-OMe) 2 (O i Pr) 6 ] ( 1 ) containing two heterochiral N atoms was synthesized from an unsymmetric N 2 O 2 ligand 2-(((2-pyridylmethyl)(2-hydroxyphenyl)amino)methyl)-4,6-di( tert -butyl)phenol (H 2 L) and characterized by single crystal X-ray diffraction. The complex 1 is an unusual tetranuclear zirconium complex with two oxo-, two methoxy- and two phenoxy-bridges. The four zirconium atoms are unequivalently coordinated. Two Zr atoms are 7-coordinate in a distorted pentagonal bipyramidal geometry, and another two Zr atoms are 6-coordinate in a distorted octahedron geometry. The ring-opening polymerization of rac -lactide catalyzed by complex 1 , gave slightly isotactic enriched polylactide with moderate polydispersities. [ABSTRACT FROM AUTHOR]