C 3N 2H 12] · [MnAl 3P 4O 17] · [H 3O]: A manganese (II)-substituted aluminophosphate with zeotype AFN topology

Abstract

Using 1,3-propyldiamine (1,3-PDA) as the structure-directing agent, a new manganese (II)-substituted aluminophosphate [C 3N 2H 12] · [MnAl 3P 4O 17] · [H 3O] (denoted MnAPO-14-PDA) containing five-coordinated Mn 2+ ions has been hydrothermally synthesized. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP and TG analyses. Differently from our recently reported MnAPO-14-DABCO built up from MnO 4(H 2O) 2 octohedra, AlO 4 and PO 4 tetrahedra, MnAPO-14-PDA is made of MnO 5 trigonal bipyramid, AlO 6 octohedra, AlO 4 and PO 4 tetrahedra. Its framework is analogous to aluminophosphate zeotype AFN in which 25% of the aluminum sites are replaced by Mn(II) atoms. The diprotonated 1,3-PDA cations and protonated H 2O molecules reside in the 8-membered ring (MR) channels. Computational simulations indicate that the substitution sites and coordination modes of Mn atoms in the framework are determined by the structure-directing agent (SDA) through the host-guest interactions. Crystal data: [C 3N 2H 12] · [MnAl 3P 4O 17] · [H 3O], triclinic P-1 (No.2), a = 9.799(3) Å, b = 9.799(3) Å, c = 11.203(4) Å, α = 72.708(4)°, β = 72.708(4)°, γ = 88.11(0)°, Z = 2, R 1 = 0.0775 ( I > 2 σ( I)) and wR 2 = 0.2079 (all data).