NITRIDO SODALITES .1. SYNTHESIS, CRYSTAL-STRUCTURE, AND PROPERTIES OF ZN7-XH2X[P12N24]CL-2 WITH 0-LESS-THAN-OR-EQUAL-TO-X-LESS-THAN-OR-EQUAL-TO-3

The nitrido sodalites Zn7-xH2x[P12N24]Cl-2 with 0 less than or equal to x less than or equal to 3 are obtained by heterogeneous pressure-ammonolysis of P3N5 at presence of ZnCl2 (T = 650 degrees C). These compounds are available too by reaction of ZnCl2, (PNCl2)(3), and NH4Cl at 700 degrees C. The crystal structures of four representatives of the above mentioned compounds have been refined by the Rietveld full-profile technique using X-ray powder diffractometer data (I(4) over bar3$ m, a = 821.61(4) to 824.21(1) pm, Z = 1). In the solid a three-dimensional framework of corner-sharing PN4-tetrahedra occurs (P-N: 163.6 pm, P-N-P: 125.6 degrees, mean values) which is isosteric with the sodalite type of structure. In the center of the beta-cages Cl- ions have been found, which are tetrahedrally coordinated by Zn2+ ions. The Zn2+ ions are statistically disordered. According to the phase-width observed (0 less than or equal to x less than or equal to 3) the Zn2+ ions may be partially replaced each by two hydrogen atoms which on the other hand are covalently bonded to nitrogen atoms of the P-N framework. The IR-spectra of these compounds show characteristic vibrations.