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Hydrothermal Synthesis and Characterization of Two New Zinc Phosphates Assembled about a Chiral Metal Complex: [Co II (en) 3 ] 2 [Zn 6 P 8 O 32 H 8 ] and [Co III (en) 3 ][Zn 8 P 6 O 24 Cl]·2H 2 O

2001; American Chemical Society; Volume: 13; Issue: 9 Linguagem: Inglês

10.1021/cm010302f

1520-5002

Jihong Yu, Yu Wang, Zhan Shi, Ruren Xu,

Polyoxometalates: Synthesis and Applications

A racemic mixture of the chiral metal complex Co(en)3Cl3 has been used in the hydrothermal synthesis of the layered compound [CoII(en)3]2[Zn6P8O32H8] (1) and the three-dimensional connected framework compound [CoIII(en)3][Zn8P6O24Cl]·2H2O (2). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by X-ray powder diffraction, ICP, elemental, and TG analyses. The structure of 1 consists of vertex-linking ZnO4 and PO3(OH) tetrahedral units forming macroanionic sheets with 4.6.8 nets. The framework structure of 2 built up of ZnO4, ZnO3Cl, and PO4 tetrahedra can be viewed as stacking of the zinc phosphate layers along the c axis linked by Cl atoms as pillars to generate intersecting tunnels with 12-membered-ring windows. Both structures 1 and 2 contain chiral structural motifs, the chiral characters of which are believed to be transferred from the chiral metal complex. The enantiomers of Co(en)3Cl3 are separated as Δ and Λ configurations in the structures of both 1 and 2 and interact with the inorganic hosts through H-bonding interactions. Crystal data: 1, monoclinic, C2/c, a = 16.623(2) Å, b = 30.589 (5) Å, c = 17.441(2) Å, β = 90.35(1)°, Z = 8; 2, trigonal, P-31c, a = 8.8775(7) Å, c = 23.775(3) Å, Z = 2.