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Volume 65 
Part 8 
Pages i63-i64  
August 2009  

Received 8 July 2009
Accepted 13 July 2009
Online 18 July 2009


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Key indicators
Powder X-ray study
T = 293 K
Mean [sigma](P-O) = 0.017 Å
Disorder in main residue
R = 0.054
wR = 0.071
Data-to-parameter ratio = 11.0
Details

Rietveld refinement of langbeinite-type K2YHf(PO4)3

Ivan V. Ogorodnyk,a Igor V. Zatovskya* and Nikolay S. Slobodyanika

aDepartment of Inorganic Chemistry, Taras Shevchenko National University, 64 Volodymyrska Str., 01601 Kyiv, Ukraine
Correspondence e-mail: zvigo@yandex.ru

Potassium yttrium hafnium tris(orthophosphate) belongs to the langbeinite-family and is built up from [MO6] octahedra [in which the positions of the two independent M sites are mutually occupied by Y and Hf in a 0.605 (10):0.395 (10) ratio] and [PO4] tetrahedra connected via vertices into a three-dimensional framework. This framework is penetrated by large closed cavities in which the two independent K atoms are located; one of the K atoms is nine-coordinated and the other is 12-coordinated by surrounding O atoms. The K, Y and Hf atoms lie on threefold rotation axes, whereas the P and O atoms are located in general positions.

Related literature

For the structure of the mineral langbeinite, see: K2Mg2(SO4)3 (Zemann & Zemann, 1957[Zemann, A. & Zemann, J. (1957). Acta Cryst. 10, 409-413.]). For powder diffraction investigations and Rietveld refinements of phosphate-based langbeinites, see: K2MZr(PO4)3, M = Y, Gd (Wulff et al., 1992[Wulff, H., Guth, U. & Loescher, B. (1992). Powder Diffr. 7, 103-106.]); K2FeZr(PO4)3 (Orlova et al., 2003[Orlova, A. I., Trubach, I. G., Kurazhkovskaya, V. S., Pertierra, P., Salvado, M. A., Garcia-Granda, S., Khainakov, S. A. & Garcia, J. R. (2003). J. Solid State Chem. 173, 314-318.]); K2LnZr(PO4)3, Ln = Ce-Lu (Trubach et al., 2004[Trubach, I. G., Beskrovnyi, A. I., Orlova, A. I., Orlova, V. A. & Kurazhkovskaya, V. S. (2004). Crystallogr. Rep. 49, 614-618.]). Hafnium-containing phosphate langbeinites are reported for K2BiHf(PO4)3 (Losilla et al., 1998[Losilla, E. R., Bruque, S., Aranda, M. A. G., Moreno-Real, L., Morin, E. & Quarton, M. (1998). Solid State Ionics, 112, 53-62.]) and K1.93Mn0.53Hf1.47(PO4)3 (Ogorodnyk et al., 2007a[Ogorodnyk, I. V., Zatovsky, I. V., Baumer, V. N., Slobodyanik, N. S., Shishkin, O. V. & Vorona, I. P. (2007a). J. Solid State Chem. 180, 2838-2844.]). For the synthesis of zirconium- or hafnium-containing langbeinite-related phosphates from fluoride precursors using flux techniques, see: Ogorodnyk et al. (2007a[Ogorodnyk, I. V., Zatovsky, I. V., Baumer, V. N., Slobodyanik, N. S., Shishkin, O. V. & Vorona, I. P. (2007a). J. Solid State Chem. 180, 2838-2844.],b[Ogorodnyk, I. V., Baumer, V. N., Zatovsky, I. V., Slobodyanik, N. S., Shishkin, O. V. & Domasevitch, K. V. (2007b). Acta Cryst. B63, 819-827.]). Parameters needed to calculate bond-valence sums were taken from Brown & Altermatt (1985[Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.]) and Brese & O'Keeffe (1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]), respectively. For ionic radii, see: Shannon (1976[Shannon, R. D. (1976). Acta Cryst. A32, 751-767.]). For crystallographic background, see: Boultif & Louër (2004[Boultif, A. & Louër, D. (2004). J. Appl. Cryst. 37, 724-731.]).

Experimental

Crystal data

  • K2YHf(PO4)3

  • Mr = 630.51

  • Cubic, P 21 3

  • a = 10.30748 (9) Å

  • V = 1095.11 (2) Å3

  • Z = 4

  • Cu K[alpha] radiation

  • T = 293 K

  • Specimen shape: flat sheet

  • 15 × 15 × 1 mm

  • Specimen prepared at 101.3 kPa

  • Specimen prepared at 293 K

  • Particle morphology: isometric, colourless
Data collection

  • Shimadzu XRD-6000 diffractometer

  • Specimen mounting: glass container

  • Specimen mounted in reflection mode

  • Scan method: step

  • 2[theta]min = 5.0, 2[theta]max = 105.0°

  • Increment in 2[theta] = 0.02°
Refinement

  • Rp = 5.375

  • Rwp = 7.075

  • Rexp = 2.809

  • RB = 4.248

  • S = 2.51

  • Wavelength of incident radiation: 1.540530 Å

  • Profile function: Thompson-Cox-Hastings pseudo-Voigt with axial divergence asymmetry (Thompson et al., 1987[Thompson, P., Cox, D. E. & Hastings, J. B. (1987). J. Appl. Cryst. 20, 79-83.])

  • 528 reflections

  • 48 parameters

Table 1
Selected geometric parameters (Å, °). M = Hf, Y

K1-O1i 2.981 (16)
K1-O2ii 3.345 (14)
K1-O4ii 3.413 (16)
K2-O3ii 2.907 (14)
K2-O2iii 2.912 (14)
K2-O4ii 3.207 (17)
K2-O4iii 3.336 (17)
M1-O1 2.148 (14)
M1-O2iv 2.085 (15)
M2-O3i 2.211 (14)
M2-O4 2.113 (17)
P1-O1 1.518 (16)
P1-O2 1.621 (17)
P1-O3 1.470 (16)
P1-O4 1.497 (19)
O1-P1-O2 100.5 (9)
O1-P1-O3 113.0 (9)
O1-P1-O4 106.9 (9)
O2-P1-O3 121.4 (8)
O2-P1-O4 107.7 (9)
O3-P1-O4 106.5 (9)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]; (iii) [-z+1, x+{\script{1\over 2}}, -y+{\script{3\over 2}}]; (iv) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z].

Data collection: PCXRD (Shimadzu, 2006[Shimadzu (2006). PCXRD. Shimadzu Corporation, Kyoto, Japan.]); cell refinement: FULLPROF (Rodriguez-Carvajal, 2006[Rodriguez-Carvajal, J. (2006). FULLPROF. Laboratoire Le'on Brillouin (CEA-CNRS), France.]); data reduction: FULLPROF; method used to solve structure: coordinates taken from an isotypic structure; program(s) used to refine structure: FULLPROF; molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and enCIFer (Allen et al., 2004[Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338.]).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2244 ).

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338.  [CrossRef] [ChemPort] [details]
Boultif, A. & Louër, D. (2004). J. Appl. Cryst. 37, 724-731.  [CrossRef] [ChemPort] [details]
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.  [CrossRef] [details]
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.  [CrossRef] [details]
Losilla, E. R., Bruque, S., Aranda, M. A. G., Moreno-Real, L., Morin, E. & Quarton, M. (1998). Solid State Ionics, 112, 53-62.  [CrossRef] [ChemPort]
Ogorodnyk, I. V., Baumer, V. N., Zatovsky, I. V., Slobodyanik, N. S., Shishkin, O. V. & Domasevitch, K. V. (2007b). Acta Cryst. B63, 819-827.  [CrossRef] [details]
Ogorodnyk, I. V., Zatovsky, I. V., Baumer, V. N., Slobodyanik, N. S., Shishkin, O. V. & Vorona, I. P. (2007a). J. Solid State Chem. 180, 2838-2844.  [CrossRef] [ChemPort]
Orlova, A. I., Trubach, I. G., Kurazhkovskaya, V. S., Pertierra, P., Salvado, M. A., Garcia-Granda, S., Khainakov, S. A. & Garcia, J. R. (2003). J. Solid State Chem. 173, 314-318.  [CrossRef] [ChemPort]
Rodriguez-Carvajal, J. (2006). FULLPROF. Laboratoire Le'on Brillouin (CEA-CNRS), France.
Shannon, R. D. (1976). Acta Cryst. A32, 751-767.  [CrossRef] [details]
Shimadzu (2006). PCXRD. Shimadzu Corporation, Kyoto, Japan.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [CrossRef] [details]
Thompson, P., Cox, D. E. & Hastings, J. B. (1987). J. Appl. Cryst. 20, 79-83.  [CrossRef] [ChemPort] [details]
Trubach, I. G., Beskrovnyi, A. I., Orlova, A. I., Orlova, V. A. & Kurazhkovskaya, V. S. (2004). Crystallogr. Rep. 49, 614-618.  [CrossRef] [ChemPort]
Wulff, H., Guth, U. & Loescher, B. (1992). Powder Diffr. 7, 103-106.  [ChemPort]
Zemann, A. & Zemann, J. (1957). Acta Cryst. 10, 409-413.  [CrossRef] [ChemPort] [details]

Acta Cryst (2009). E65, i63-i64   [ doi:10.1107/S1600536809027573 ]

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