The crystalline chiral zirconium phosphonates with α, γ-type structure, formulated as Zr(PO 4) 0.6(HPO 4) 0.1(O 3PCH 2NHC 4H 7COO-) 0.55(O 3PCH 2NHC 3H 7COOH) 0.55F 0.55·H 2O(mix-ZrPMP, [α] 25 D=-36°) and Zr(PO 4) 0.6(HPO 4) 0.1(O 3PCH 2NHCH 2SC 2H 3COO-) 0.55(O 3PCH 2NHCH 2S-C 2H 3COOH) 0.55F 0.55·2.0H 2O(mix-ZrPMT, [α] 25 D=-39°), were obtained in situ by reaction of N-phosphonomethyl-L-proline(H 3PMP) and N-phosphonomethyl-1,3-thiazolidine-4-carboxylic acid(H 3PMTA) with ZrOCl 2·8H 2O in the presence of HF at 90 ℃, respectively. The heterocycle thiazolidine was integrated onto metal-organic frameworks. Of mix-ZrPMP and mix-ZrPMT, the CO 2H, CO- 2 and NH+ groups are remained in layered structures of mixed-type.
A novel supramolecular sodium N,N-piperazinebis(methylenephosphonate) Na 2[(HO 3PCH 2)\5NC 4H 8N(CH 2PO 3H)](H 2O) 8·2H 2O, self-assembled into infinite 1D chains, was synthesized by the reaction of N,N-piperazine bis(methylenephosphonic acid) with NaOH. Its structure was characterized by single crystal X-ray diffraction, ICP and elemental analysis. The compound crystallizes in triclinic system, space group P1 with a=0.659 06(2) nm, b=0.726 73(2) nm, c= 1.158 25(4) nm, α=79.751(2)°, β=75.833(2)°, γ=74.122(2)°, V=0.513 68(3) nm 3, Z=2, D c=1.611 Mg/m 3, μ=0.331 mm -1, F(000)=264, S=1.098, R 1=0.045 2, wR=0.136 0. In the crystal, edge sharing octahedron Na 2O 10 dimers and tetrahedron PO 3C are assembled to an 1D chain via the bridges of heterocycle. 3D supramolecular framework is self-assembled from 1D chains through H-bonds.
