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Volume 69 
Part 5 
Page i23  
May 2013  

Received 14 February 2013
Accepted 21 March 2013
Online 5 April 2013

Key indicators
Powder X-ray study
T = 293 K
Mean [sigma](P-O) = 0.050 Å
R = 0.094
wR = 0.125
Data-to-parameter ratio = 30.3
Details
Open access

Rietveld refinement of AgCa10(PO4)7 from X-ray powder data

aDepartment of Inorganic Chemistry, Taras Shevchenko National University, 64/13 Volodymyrska str., 01601 Kyiv, Ukraine
Correspondence e-mail: Strutynska_N@bigmir.net

Polycrystalline silver(I) decacalcium heptakis(orthophosphate), AgCa10(PO4)7, was obtained by solid-state reaction. It is isotopic with members of the series MCa10(PO4)7 (M = Li, Na, K and Cs), and is closely related to the structure of [beta]-Ca3(PO4)2. The crystal structure of the title compound is built up from a framework of [CaO9] and two [CaO8] polyhedra, one [CaO6] octahedron (site symmetry 3.) and three PO4 tetrahedra (one with site symmetry 3.). The Ag+ cation is likewise located on a threefold rotation axis and resides in the cavities of the rigid [Ca10(PO4)7]- framework. It is surrounded by three O atoms in an almost regular triangular environment.

Related literature

For the structure of the mineral whitlockite, see: Calvo & Gopal (1975[Calvo, C. & Gopal, R. (1975). Am. Mineral. 60, 120-133.]); Yashima et al. (2003[Yashima, M., Sakai, A., Kamiyama, T. & Hoshikawa, A. (2003). J. Solid State Chem. 175, 272-277.]). For powder diffraction studies and Rietveld refinements of phosphate-based whitlockite-related compounds, see: Lazoryak et al. (1996[Lazoryak, B. I., Morozov, V. A., Belik, A. A., Khasanov, S. S. & Shekhtman, V. Sh. (1996). J. Solid State Chem. 122, 15-21.]); Morozov et al. (2000[Morozov, V. A., Belik, A. A., Kotov, R. N., Presnyakov, I. A., Khasanov, S. S. & Lazoryak, B. I. (2000). Crystallogr. Rep. 45, 13-20.], 2002[Morozov, V. A., Belik, A. A., Stefanovich, S. Yu., Grebenev, V. V., Lebedev, O. I., Tendeloo, G. V. & Lazoryak, B. I. (2002). J. Solid State Chem. 165, 278-288.]); Zatovsky et al. (2007[Zatovsky, I. V., Strutynska, N. Y., Baumer, V. N., Shishkin, O. V. & Slobodyanik, N. S. (2007). Acta Cryst. E63, i180-i181.], 2010[Zatovsky, I. V., Ogorodnyk, I. V., Strutynska, N. Y., Slobodyanik, N. S. & Sharkina, N. O. (2010). Acta Cryst. E66, i41-i42.], 2011[Zatovsky, I. V., Strutynska, N. Yu., Baumer, V. N., Slobodyanik, N. S., Ogorodnyk, I. V. & Shishkin, O. V. (2011). J. Solid State Chem. 184, 705-711.]). For physical properties of these materials, see: Dou et al. (2011[Dou, X., Zhao, W., Song, E., Zhou, G., Yi, C. & Zhou, M. (2011). Spectrochim. Acta Part A, 78, 821-825.]); Enhai et al. (2011[Enhai, S., Weiren, Z., Guoxiong, Z., Xihua, D., Chunyu, Y. I. & Minkang, Z. (2011). J. Rare Earths, 29, 440-443.]); Lazoryak et al. (2004[Lazoryak, B. I., Morozov, V. A., Belik, A. A., Stefanovich, S. Yu., Grebenev, V. V., Leonidov, I. A., Mitberg, E. B., Davydov, S. A., Lebedev, O. I. & Tendeloo, G. V. (2004). Solid State Sci. 6, 185-195.]); Teterskii et al. (2005[Teterskii, A. V., Morozov, V. A., Stefanovich, S. Yu. & Lazoryak, B. I. (2005). Russ. J. Inorg. Chem. 50, 1072-1076.]); Zhang et al. (2011[Zhang, J., Wang, Y., Wen, Y., Zhang, F. & Liu, B. (2011). J. Alloys Compd, 509, 4649-4652.]). For the crystal structure of isotypic KCa10(PO4)7, see: Sandström & Boström (2006[Sandström, M. H. & Boström, D. (2006). Acta Cryst. E62, i253-i255.]). For bond-valence calculations, see: Brown (2002[Brown, I. D. (2002). In The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. Oxford University Press.]).

Experimental

Crystal data
  • AgCa10(PO4)7

  • Mr = 1173.46

  • Trigonal, R 3c

  • a = 10.43723 (5) Å

  • c = 37.3379 (7) Å

  • V = 3522.50 (7) Å3

  • Z = 6

  • Cu K[alpha] radiation, [lambda] = 1.540560 Å

  • T = 293 K

  • Flat sheet, 25 × 25 mm

Data collection
  • Shimadzu LabX XRD-6000 diffractometer

  • Specimen mounting: glass container

  • Data collection mode: reflection

  • Scan method: step

  • 2[theta]min = 9.045°, 2[theta]max = 100.045°, 2[theta]step = 0.020°

Refinement
  • Rp = 0.094

  • Rwp = 0.125

  • Rexp = 0.042

  • RBragg = 0.051

  • R(F) = 0.038

  • [chi]2 = 8.821

  • 4551 data points

  • 150 parameters

  • 3 restraints

Data collection: PCXRD (Shimadzu, 2006[Shimadzu (2006). PCXRD. Shimadzu Corporation, Kyoto, Japan.]); cell refinement: DICVOL (Boultif & Louër, 2004[Boultif, A. & Louër, D. (2004). J. Appl. Cryst. 37, 724-731.]); data reduction: FULLPROF (Rodriguez-Carvajal, 2006[Rodriguez-Carvajal, J. (2006). FULLPROF. Laboratoire Léon Brillouin (CEA-CNRS), France.]); program(s) used to solve structure: FULLPROF (Rodriguez-Carvajal, 2006[Rodriguez-Carvajal, J. (2006). FULLPROF. Laboratoire Léon Brillouin (CEA-CNRS), France.]); program(s) used to refine structure: FULLPROF (Rodriguez-Carvajal, 2006[Rodriguez-Carvajal, J. (2006). FULLPROF. Laboratoire Léon Brillouin (CEA-CNRS), France.]); 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: WM2726 ).


References

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Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Brown, I. D. (2002). In The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. Oxford University Press.
Calvo, C. & Gopal, R. (1975). Am. Mineral. 60, 120-133.  [ChemPort]
Dou, X., Zhao, W., Song, E., Zhou, G., Yi, C. & Zhou, M. (2011). Spectrochim. Acta Part A, 78, 821-825.
Enhai, S., Weiren, Z., Guoxiong, Z., Xihua, D., Chunyu, Y. I. & Minkang, Z. (2011). J. Rare Earths, 29, 440-443.
Lazoryak, B. I., Morozov, V. A., Belik, A. A., Khasanov, S. S. & Shekhtman, V. Sh. (1996). J. Solid State Chem. 122, 15-21.  [CrossRef] [ChemPort] [ISI]
Lazoryak, B. I., Morozov, V. A., Belik, A. A., Stefanovich, S. Yu., Grebenev, V. V., Leonidov, I. A., Mitberg, E. B., Davydov, S. A., Lebedev, O. I. & Tendeloo, G. V. (2004). Solid State Sci. 6, 185-195.  [ISI] [CrossRef] [ChemPort]
Morozov, V. A., Belik, A. A., Kotov, R. N., Presnyakov, I. A., Khasanov, S. S. & Lazoryak, B. I. (2000). Crystallogr. Rep. 45, 13-20.  [ISI] [CrossRef]
Morozov, V. A., Belik, A. A., Stefanovich, S. Yu., Grebenev, V. V., Lebedev, O. I., Tendeloo, G. V. & Lazoryak, B. I. (2002). J. Solid State Chem. 165, 278-288.  [ISI] [CrossRef] [ChemPort]
Rodriguez-Carvajal, J. (2006). FULLPROF. Laboratoire Léon Brillouin (CEA-CNRS), France.
Sandström, M. H. & Boström, D. (2006). Acta Cryst. E62, i253-i255.  [CrossRef] [details]
Shimadzu (2006). PCXRD. Shimadzu Corporation, Kyoto, Japan.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [ISI] [CrossRef] [ChemPort] [details]
Teterskii, A. V., Morozov, V. A., Stefanovich, S. Yu. & Lazoryak, B. I. (2005). Russ. J. Inorg. Chem. 50, 1072-1076.  [ChemPort]
Yashima, M., Sakai, A., Kamiyama, T. & Hoshikawa, A. (2003). J. Solid State Chem. 175, 272-277.  [ISI] [CrossRef] [ChemPort]
Zatovsky, I. V., Ogorodnyk, I. V., Strutynska, N. Y., Slobodyanik, N. S. & Sharkina, N. O. (2010). Acta Cryst. E66, i41-i42.  [CrossRef] [ChemPort] [details]
Zatovsky, I. V., Strutynska, N. Y., Baumer, V. N., Shishkin, O. V. & Slobodyanik, N. S. (2007). Acta Cryst. E63, i180-i181.  [CrossRef] [ChemPort] [details]
Zatovsky, I. V., Strutynska, N. Yu., Baumer, V. N., Slobodyanik, N. S., Ogorodnyk, I. V. & Shishkin, O. V. (2011). J. Solid State Chem. 184, 705-711.  [ISI] [CrossRef] [ChemPort]
Zhang, J., Wang, Y., Wen, Y., Zhang, F. & Liu, B. (2011). J. Alloys Compd, 509, 4649-4652.  [ISI] [CrossRef] [ChemPort]


Acta Cryst (2013). E69, i23  [ doi:10.1107/S1600536813007848 ]

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