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.
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 new layered fluoroaluminophosphate \\[Al2（PO4）2（H2O）2F2\]（compound Ⅰ） was synthesized hydrothermally. It crystallizes in the monoclinic space group P21/c with a=1.102 40（7） nm, （b=0.695 51（4） nm,） c=0.928 05（5） nm, β=111.027（3）°, Z=6, R1=0.037 9, wR2=0.079 2（all data）. Its structure contains \[Al2（PO4）2（H2O）2F2\]2- macroanonic sheets built up from PO3（O） tetrahedra and AlO3F2（H2O） octahedra to form three-, four-, six-membered ring-net stacked sheets in an AAAA sequence along \ direction. The sheets are held together by diprotonated piperazine cations decomposed from 1-methylpiperazine through extensive hydrogen bonds.
Three open\|framework zinc germanophosphates have been synthesized from ethylene glycol systems of Zn(Ac)\-2·2H\-2O\|H\-3PO\-4\|\%R\%\|GeO\-2\|Py\|EG, where \%R\% stands for an amine and EG for ethylene glycol. It was found that by selecting proper amines as structure\|directing templates during crystallization open\|framework zinc germanophosphates were synthesized. The structures of the zinc germanophosphates were characterized by X\|ray diffraction(XRD), scanning electron microscopy(SEM), inductively coupled plasma(ICP) analysis, infrared spectroscopy(IR).
