Cover Image

Structure, Infrared and Raman spectroscopic studies of the new Ba(NbV0.5MIII0.5)(PO4)2 (MIII = Al, Cr, Fe, In) yavapaiite compounds ‘series

Rachid Fakhreddine, Abderrahim Aatiq


Synthesis and structural study of the new Ba(NbV0.50MIII0.50)(PO4)2 (MIII = Al, Cr, Fe, In) phosphates, abbreviated as [BaNbM], were reported here for the first time. Structures of [BaNbM] compounds, obtained by solid-state reaction in air atmosphere, were determined at room temperature from X-ray powder diffraction using the Rietveld method. The four studied compoundsfeature the yavapaiite-type structure, with space group C2/m ( , N°12) and Z = 2. Their framework can be described as consisting of dense slabs of Nb(M)O6 octahedra and PO4 tetrahedra interconnected via corner-sharing, alternating along the c‑axis with layers of Ba cations in ten-fold coordination. Raman and Infrared spectroscopic study were used to obtain further structural information about the nature of bonding in selected compositions. Assignments of Nb‑O, M‑O and P‑O Raman and Infrared bands, in [BaNbM] compounds, were based on those already known in the literature for niobium and phosphates oxides. Some empirical relationships, connecting Raman stretching frequencies to the obtained Nb‑O and P‑O distance values, were also used for assignments of various Raman bands.

Full Text:



- N. Clavier, R. Podor, N. Dacheux, Crystal chemistry of the monazite structure, J. Eur. Ceram. Soc., 2011, 31, 941-976.

- J. J. Finney, N. Nagaraja Rao, The crystal structure of Chéralite, Am. Mineral., 1967, 52, 13-19.

- K. Fukuda, A. Moriyama, T. Iwata, Crystal structure, phase transition and anisotropic thermal expansion of barium zirconium diorthophosphate, BaZr(PO4)2, J. Solid State Chem., 2005, 178, 2144-2151.

- A. Leclaire, M. M. Barel, J. Chardon, B. Raveau, A Mo(IV) Monophosphate, BaMo(PO4)2, with the Yavapaiite Layer Structure, J. Solid State Chem., 1995, 116,


- K. Popa, G. Wallez, D. Bregiroux, P. Loiseau, MIIGe(PO4)2 (M=Ca, Sr, Ba) Crystal structure, phase transitions and thermal expansion, J. Solid State Chem., 2011, 184, 2629-2634.

- D. Zhao, H. Zhang, Z. Xie, W. L. Zhang, S. L. Yang, W. D. Cheng, Syntheses, crystal and electronic structures of compounds AM(PO4)2 (A = Sr, M = Ti, Sn; A = Ba, M = Sn), Dalton Trans., 2009, 27, 5310-5318.

- W. L. Zhang, C. S. Lin, Z. Z. He, H. Zhang,

Z. Z. Luo, W. D. Cheng, Syntheses of three members of A(II)M(IV)(PO4)2: luminescence properties of PbGe(PO4)2 and its Eu3+ doped powders, Cryst. Eng. Comm., 2013, 15, 7089-7094.

- G. Wallez, D. Bregiroux, K. Popa, P. E. Raison, C. Apostolidis, P. Lindqvist-Reis, R. J. M. Konings, A. F. Popa, BaAnIV(PO4)2 (AnIV = Th, Np) A New Family of Layered Double Phosphates, J. Inorg. Chem., 2011, 110-115.

- E. Morin, G. Wallez, S. Jaulmes, J. C. Couturier, M. Quarton, Structure of PbIISnIV(PO4)2: Stereochemical Activity of the Lead II Lone Pair, J. Solid State Chem., 1998, 137, 283-288.

- G. Blasse, G. J. Dirksen, The luminescence of Barium Titanium Phosphate BaTi(PO4)2, Chem. Phys. Lett., 1979, 62, 19-20.

- Z. J. Zhang, J. L. Yuan, X. J. Wang, D. B. Xiong, H. H. Chen, J. T. Zhao, Y. B. Fu, Z. M. Qi, G. B. Zhang, C. S. Shi, Luminescence properties of CaZr(PO4)2: RE (RE = Eu3+, Tb3+, Tm3+) under x-ray and VUV–UV excitation, Phys. D Appl. Phys., 2007, 40, 1910-1914.

- A. Aatiq, R. Hassine, R. Tigha, I. Saadoune, Structures of two newly synthesized A0.50SbFe(PO4)3 (A=Mn, Cd) Nasicon phases, Powder Diffr., 2005, 20, 33-39.

- A. Aatiq, R. Tigha, S. Benmokhtar, Structure, infrared and Raman spectroscopic studies of new Sr0.50SbFe (PO4)3 and SrSb0.50Fe1.50 (PO4)3 Nasicon phases, J. Mater. Sci., 2012, 47,


- A. Aatiq, R. Tigha, R. Hassine, I. Saadoune, Crystallochemistry and structural studies of two newly CaSb0.50Fe1.50(PO4)3 and Ca0.50SbFe(PO4)3 Nasicon phases, Powder Diffr., 2006, 21, 45-51.

- A. Aatiq, My R. Tigha, R. Fakhreddine,

A. Marchoud, Structure and spectroscopic characterization of the two PbSb0.5Fe1.5(PO4)3 and Pb0.5SbFe(PO4)3 phosphates with Nasicon type-structure, J. Mater. Environ. Sci., 2015, 6, 3483-3490.

- A. Aatiq, A. Marchoud, H. Bellefquih, My

R. Tigha, Structural and Raman spectroscopic studies of the two M0.50SbFe(PO4)3 (M = Mg, Ni) NASICON phases Powder Diffr., 2017, 32, 40-51.

- A. Aatiq, My R. Tigha, R. Fakhreddine,

D. Bregiroux, G. Wallez, Structure, infrared and Raman spectroscopic studies of newly synthetic AII(SbV0.50FeIII0.50)(PO4)2 (A=Ba, Sr, Pb) phosphates with yavapaiite structure Solid State Sci., 2016, 58, 44-54.

- J. Rodríguez-Carvajal, Recent advances in magnetic structure determination by neutron powder diffraction Physica B. Condensed Matter., 1993, 192, 55-69.

- B. Srinivasulu, M. Vithal, Preparation of a new family of NASICON type phosphates Ca0.5NbMP3O12 (M = Fe, Al, Ga and In) and characterization of the iron systems by Mossbauer spectroscopy Mater. Sci. Lett., 1999, 18, 1771-1773.

- A. Le Bail, H. Duroy, J. L. Fourquet, Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction, Mater. Res. Bull., 1988, 23, 447-452.

- R. D. Shannon, Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Acta Crystallographica Section A, 1988, 32,


- D. Zhao, Fa-X. Ma, H. Yang, W. Wei, Y.-C. Fan, L. Zhang, X. Xin, Structure twinning, electronic and photoluminescence properties of yavapaiite-type orthophosphate BaTi(PO4)2,

J. Phys. Chem. Solids, 2016, 99, 59–65

- I. D. Brown, D. Altermatt, Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database Acta Cryst. Section B, 1985, 41, 244-247.

- M. Th. Paques-Ledent, AIIBIV(XO4)2 Phosphates and Arsenates with Yavapaiite structure I: isostructural relationship and vibrational study, Inorg. Nucl. Chem., 1977, 39, 11-17.

- A. Ann McConnel, J. S. Aderson, C. N. R. Rao, Raman spectra of niobium oxides, A Mol. Biomol. Spectrosc., 1976, 32, 1067-1076.

- A. El Jazouli, C. Parent, J. M. Dance, G. Le Flem, P. Hagenmuller, J. C. Viala, Na4Nb(PO4)3, a material with a reversible crystal-glass transformation: Structural and optical comparison, J. Solid State Chem., 1988, 74, 377-384.

- F. D. Hardcastle, I. E. Wachs, Determination of niobium-oxygen bond distances and bond orders by Raman spectroscopy, Solid State Ion., 1991, 45, 201-213.

- L. Popović, D. de Waal, J. C. A. Boeyens, Correlation between Raman wavenumbers and P—O bond lengths in crystalline inorganic phosphates, J. Raman Spectrosc., 2005, 36,


- W. G. Fateley, F. R. Dollish, N. T. McDevitt, F.F. Bentley, Infrared and Raman selection rules for molecular and lattice vibrations the correlation method, Wiley-Interscience, New York, 1972.

- K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part A, Fifth ed, Wiley–Interscience, New York 1997.

- G. Butt, N. Sammes, G. Tompsett, A. Smirnova, O. Yamamoto, Raman spectroscopy of superionic Ti-doped Li3Fe2(PO4)3 and LiNiPO4 structures, J. Power sources, 2004, 134, 72-79.


  • There are currently no refbacks.

Copyright (c) 2019 Mediterranean Journal of Chemistry