Synthesis and crystal structure of a novel hexanuclear Zr(IV) complex with 1,10-phenanthroline including carboxylato, hydroxo, and oxo bridging

Abstract

A novel hexanuclear Zr(IV) complex, [Zr 6(O) 6(OH) 2(Ph 2CHCOO) 10(phen) 2]·4CH 3CN ( 1), where phen denotes 1,10-phenanthroline, has been prepared and characterized on the basis of elemental analysis, infrared-spectroscopy measurements, and X-ray crystallography. Complex 1 resides on a crystallographic inversion center, thus making only three of the six zirconium ions unique. The six zirconium ions are arranged in apices of an octahedron. One Zr(IV) metal ion (Zr1) is individually joined with two Zr(IV) metal ions (Zr2, Zr3) by one syn–syn bridging carboxylate group, and Zr1 has three μ 3-O and one μ 3-OH bridges through Zr2 and Zr3. The Zr2 atom is also connected by one syn–syn bridging carboxylate group through Zr3*. Moreover, Zr1 is coordinated by two nitrogen atoms of a bidentate 1,10-phenanthroline group with eight coordination. Besides these, Zr2 is coordinated by one carboxylate of a bidentate–chelate type, completing the eight coordination. The Zr3 atom is coordinated by one monodentate carboxylate oxygen, consequently has a novel seven coordination.