Hydrothermal Synthesis and Characterization of Two New Zinc Phosphates Assembled about a Chiral Metal Complex:  [CoII(en)₃]₂[Zn₆P₈O₃₂H₈] and [CoIII(en)₃][Zn₈P₆O₂₄Cl]·2H₂O

A racemic mixture of the chiral metal complex Co(en) 3 Cl 3 has been used in the hydrothermal synthesis of the layered compound [Co II (en) 3 ] 2 [Zn 6 P 8 O 32 H 8 ] ( 1 ) and the three-dimensional connected framework compound [Co III (en) 3 ][Zn 8 P 6 O 24 Cl]·2H 2 O ( 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 ZnO 4 and PO 3 (OH) tetrahedral units forming macroanionic sheets with 4.6.8 nets. The framework structure of 2 built up of ZnO 4, ZnO 3 Cl, and PO 4 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) 3 Cl 3 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, C 2/ 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 -31 c, a = 8.8775(7) Å, c = 23.775(3) Å, Z = 2.