The structure of NaPb9(PO4)(6)F(H2O)(0.33), isostructural with apatite, was determined by X-ray powder diffraction methods and the result of Rietveld refinement is P6(3)/m, a = 9.76396(8) angstrom and c = 7.27520(9) angstrom. The final refinement led to R-F = 5.4%, R-B = 6.6%. In the tunnel, the water molecule (O-w) and F- ions appear to be located in 2b and 4e sites, with occupancies of 0.028(6) and 0.075(8), respectively. In the M(1) and M(2) sites the occupancies of Pb and Na are 0.282(3)/0.051(3) and 0.467(5)/0.033(5), respectively. The formula assigned to the compound is [Pb3.38(4)Na0.62(4)](1)[Pb5.60(6)Na0.40(6)](2)(PO4)(6)F-0.90(10)(H2O)(0.33(7))square(0.77(17)), Where square = vacancy. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit-cell group analysis and by comparison with fluor and chloroapatite analogs. The result of P-31 and Na-23 magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopies confirmed the structural results. (C) 2007 Elsevier Ltd. All rights reserved.