Hydrothermal synthesis and characterization of two new zinc phosphates assembled about a chiral metal complex: [Co^II(en)₃] ₂[Zn₆P₈O₃₂H₈] and [Co^III(en)₃][Zn₈P₆O₂₄ Cl]·2H₂O

A racemic mixture of the chiral metal complex Co(en)₃Cl₃ has been used in the hydrothermal synthesis of the layered compound [Co^II(en)₃]₂[Zn₆P₈ O₃₂H₈] (1) and the three-dimensional connected framework compound [Co^III(en)₃][Zn₈P₆O₂₄ Cl]·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 ∧ 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.