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Volume 69 
Part 12 
Pages i85-i86  
December 2013  

Received 15 November 2013
Accepted 23 November 2013
Online 30 November 2013

Key indicators
Single-crystal X-ray study
T = 298 K
Mean [sigma](Co-O) = 0.003 Å
Disorder in main residue
R = 0.020
wR = 0.049
Data-to-parameter ratio = 10.0
Details
Open access

Na3Co2(As0.52P0.48)O4(As0.95P0.05)2O7

aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis ElManar, 2092 Manar II Tunis, Tunisia
Correspondence e-mail: faouzi.zid@fst.rnu.tn

The title compound, trisodium dicobalt(II) (arsenate/phosphate) (diarsenate/diphosphate), was prepared by a solid-state reaction. It is isostructural with Na3Co2AsO4As2O7. The framework shows the presence of CoX22O12 (X2 is statistically disordered with As0.95P0.05) units formed by sharing corners between Co1O6 octa­hedra and X22O7 groups. These units form layers perpendicular to [010]. Co2O6 octa­hedra and X1O4 (X1 = As0.54P0.46) tetra­hedra form Co2X1O8 chains parallel to [001]. Cohesion between layers and chains is ensured by the X22O7 groups, giving rise to a three-dimensional framework with broad tunnels, running along the a- and c-axis directions, in which the Na+ ions reside. The two Co2+ cations, the X1 site and three of the seven O atoms lie on special positions, with site symmetries 2 and m for the Co, m for the X1, and 2 and m (× 2) for the O sites. One of two Na atoms is disordered over three special positions [occupancy ratios 0.877 (10):0.110 (13):0.066 (9)] and the other is in a general position with full occupancy. A comparison between structures such as K2CdP2O7, [alpha]-NaTiP2O7 and K2MoO2P2O7 is made. The proposed structural model is supported by charge-distribution (CHARDI) analysis and bond-valence-sum (BVS) calculations. The distortion of the coordination polyhedra is analyzed by means of the effective coordination number.

Related literature

For isotypic structures, see: Ben Smail & Jouini (2005[Ben Smail, R. & Jouini, T. (2005). Anal. Chem. 30, 119-132.]); Guesmi & Driss (2012[Guesmi, A. & Driss, A. (2012). Acta Cryst. E68, i58.]). For related structures, see: Ben Smail & Jouini (2004[Ben Smail, R. & Jouini, T. (2004). Acta Cryst. E60, i1-i2.]); Boughzala et al. (1997[Boughzala, H., Driss, A. & Jouini, T. (1997). Acta Cryst. C53, 3-5.]); Faggiani & Calvo (1976[Faggiani, R. & Calvo, C. (1976). Can. J. Chem. 54, 3319-3324.]); Leclaire et al. (1988[Leclaire, A., Benmoussa, A., Borel, M. M., Grandin, A. & Raveau, B. (1988). J. Solid State Chem. 77, 299-305.]); Geoffroy et al. (2011[Geoffroy, H., Anubhav, J., Shyue Ping, O., Byoungwoo, K., Charles, M., Robert, D. & Gerbrand, C. (2011). Chem. Mater. 23, 3495-3508.]); Rissouli et al. (1996[Rissouli, K., Benkhouja, K., Sadel, A., Bettach, M., Zahir, M., Giorgi, M. & Pierrot, M. (1996). Acta Cryst. C52, 2960-2963.]); Zid et al. (2003[Zid, M. F., Driss, A. & Jouini, T. (2003). Acta Cryst. E59, i65-i67.]). For bond-valence analysis, see: Brown (2002[Brown, I. D. (2002). The Chemical Bond in Inorganic Chemistry - The Bond Valence Model. IUCr Monographs on Crystallography, No. 12. Oxford University Press.]); Adams (2003[Adams, S. (2003). softBV. University of Göttingen, Germany. http://kristall.uni-mki.gwdg .de/softBV/]). For the charge distribution method, see: Nespolo et al. (2001[Nespolo, M., Ferraris, G., Ivaldi, G. & Hoppe, R. (2001). Acta Cryst. B57, 652-664.]); Nespolo (2001[Nespolo, M. (2001). CHARDI-IT, CRM2. University Henri Poincaré Nancy I, France.]); Guesmi et al. (2006[Guesmi, A., Nespolo, M. & Driss, A. (2006). J. Solid State Chem. 179, 2466-2471.]).

Experimental

Crystal data
  • Na3Co2(As0.52P0.48)O4(As0.95P0.05)2O7

  • Mr = 562.32

  • Monoclinic, C 2/m

  • a = 10.3982 (9) Å

  • b = 16.087 (2) Å

  • c = 6.4421 (6) Å

  • [beta] = 120.425 (9)°

  • V = 929.21 (17) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 12.44 mm-1

  • T = 298 K

  • 0.26 × 0.18 × 0.16 mm

Data collection
  • Enraf-Nonius CAD-4 diffractometer

  • Absorption correction: [psi] scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.077, Tmax = 0.138

  • 2212 measured reflections

  • 1052 independent reflections

  • 974 reflections with I > 2[sigma](I)

  • Rint = 0.027

  • 2 standard reflections every 120 reflections intensity decay: 1.4%

Refinement
  • R[F2 > 2[sigma](F2)] = 0.020

  • wR(F2) = 0.049

  • S = 1.15

  • 1052 reflections

  • 105 parameters

  • 3 restraints

  • [Delta][rho]max = 0.61 e Å-3

  • [Delta][rho]min = -0.61 e Å-3

Data collection: CAD-4 EXPRESS (Duisenberg, 1992[Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92-96.]; Macícek & Yordanov, 1992[Macícek, J. & Yordanov, A. (1992). J. Appl. Cryst. 25, 73-80.]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg & Putz, 2001[Brandenburg, K. & Putz, H. (2001). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BR2232 ).


References

Adams, S. (2003). softBV. University of Göttingen, Germany. http://kristall.uni-mki.gwdg .de/softBV/
Ben Smail, R. & Jouini, T. (2004). Acta Cryst. E60, i1-i2.  [CrossRef] [ChemPort] [IUCr Journals]
Ben Smail, R. & Jouini, T. (2005). Anal. Chem. 30, 119-132.  [ChemPort]
Boughzala, H., Driss, A. & Jouini, T. (1997). Acta Cryst. C53, 3-5.  [CrossRef] [IUCr Journals]
Brandenburg, K. & Putz, H. (2001). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Brown, I. D. (2002). The Chemical Bond in Inorganic Chemistry - The Bond Valence Model. IUCr Monographs on Crystallography, No. 12. Oxford University Press.
Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92-96.  [CrossRef] [ChemPort] [Web of Science] [IUCr Journals]
Faggiani, R. & Calvo, C. (1976). Can. J. Chem. 54, 3319-3324.  [CrossRef] [ChemPort] [Web of Science]
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Geoffroy, H., Anubhav, J., Shyue Ping, O., Byoungwoo, K., Charles, M., Robert, D. & Gerbrand, C. (2011). Chem. Mater. 23, 3495-3508.
Guesmi, A. & Driss, A. (2012). Acta Cryst. E68, i58.  [CrossRef] [IUCr Journals]
Guesmi, A., Nespolo, M. & Driss, A. (2006). J. Solid State Chem. 179, 2466-2471.  [Web of Science] [CrossRef] [ChemPort]
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
Leclaire, A., Benmoussa, A., Borel, M. M., Grandin, A. & Raveau, B. (1988). J. Solid State Chem. 77, 299-305.  [CrossRef] [ChemPort] [Web of Science]
Macícek, J. & Yordanov, A. (1992). J. Appl. Cryst. 25, 73-80.  [CrossRef] [Web of Science] [IUCr Journals]
Nespolo, M. (2001). CHARDI-IT, CRM2. University Henri Poincaré Nancy I, France.
Nespolo, M., Ferraris, G., Ivaldi, G. & Hoppe, R. (2001). Acta Cryst. B57, 652-664.  [CrossRef] [ChemPort] [IUCr Journals]
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.  [CrossRef] [IUCr Journals]
Rissouli, K., Benkhouja, K., Sadel, A., Bettach, M., Zahir, M., Giorgi, M. & Pierrot, M. (1996). Acta Cryst. C52, 2960-2963.  [CrossRef] [IUCr Journals]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Zid, M. F., Driss, A. & Jouini, T. (2003). Acta Cryst. E59, i65-i67.  [CrossRef] [ChemPort] [IUCr Journals]


Acta Cryst (2013). E69, i85-i86   [ doi:10.1107/S1600536813032029 ]

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