New zirconium phosphate fluorides with 3D-framework

From aqueous solutions of ZrOCl2, H3PO4, HF, and various amines. two new co mpounds of the general formula [amH(2)](1/2)[Zr-2(HPO4)(PO4)(2)F].nH(2)O (I : am = N,N-dimethylethylenediamine, n = 0,5; II: am = N,N-dimethyl-1,3-D(i) aminopropane. n = 0) adopting the ZrPOF-1 structure type have been synthesi zed under hydrothermal conditions. In contrast to the monoclinic ZrPOF-1. b oth compounds crystallize in the space group P (1) over bar with a = 6.611( 3), b = 9.109(4), c = 11.560(5) A, a = 85.62(4), beta = 89.60(4), gamma = 7 0.57( 1)degrees in I, and a = 6.616(2), b = 9.045(3), c = 11.565(4) Angstro m, alpha = 85.26(4), beta = 88.86(4), gamma = 71.46(4)degrees in II. Compou nd III (am = ethylenediamine, n = 0) has been obtained by dehydration of Zr POF-1 and occurs in the space group P1 with a = 6.605(2), b = 8.787(3), c = 11.499(5) Angstrom, alpha = 93.07(4), beta = 90.42(4) and gamma =101.66(4) degrees. The structural motifs of the frameworks of the three compounds hav e much in common. The template and the PO3OH tetrahedra in I and II are dis ordered. Differences in the water content in both compounds are due to diff erences in the chain lengths of the amines. The absence of crystal water in compound III breaks the template disordering which is present in ZrPOF-1. The rotation of the PO3OH tetrahedra in II and III compared with I and ZrPO F-1 is discussed in regard with the absence of stabilizing H-bridges in the farmer compounds.