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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): i67.
Published online 2009 August 15. doi:  10.1107/S160053680903147X
PMCID: PMC2970136

Cs2Bi(PO4)(WO4)

Abstract

Dicaesium bis­muth(III) phosphate(V) tungstate(VI), Cs2Bi(PO4)(WO4), has been synthesized during complex investigation in a molten pseudo-quaternary Cs2O–Bi2O3–P2O5–WO3 system. It is isotypic with K2Bi(PO4)(WO4). The three-dimensional framework is built up from [Bi(PO4)(WO4)] nets, which are organized by adhesion of [BiPO4] layers and [WO4] tetra­hedra above and below of those layers. The inter­stitial space is occupied by Cs atoms. Bi, W and P atoms lie on crystallographic twofold axes.

Related literature

For the isotypic potassium analogue, see: Zatovsky et al. (2006 [triangle]). For a related structure, see: Terebilenko et al. (2008 [triangle]). For caesium coordination, see Borel et al. (2000 [triangle]); Yakubovich et al. (2006 [triangle])

Experimental

Crystal data

  • Cs2Bi(PO4)(WO4)
  • M r = 817.61
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-00i67-efi1.jpg
  • a = 21.3144 (10) Å
  • b = 12.6352 (5) Å
  • c = 7.1412 (3) Å
  • V = 1923.21 (14) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 37.87 mm−1
  • T = 293 K
  • 0.08 × 0.07 × 0.05 mm

Data collection

  • Oxford Diffraction XCalibur-3 diffractometer
  • Absorption correction: multi-scan (Blessing, 1995 [triangle]) T min = 0.061, T max = 0.174 (expected range = 0.053–0.151)
  • 10697 measured reflections
  • 1396 independent reflections
  • 1227 reflections with I > 2σ(I)
  • R int = 0.156

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.115
  • S = 1.21
  • 1396 reflections
  • 61 parameters
  • Δρmax = 2.17 e Å−3
  • Δρmin = −2.63 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 [triangle]); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 1999 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and enCIFer (Allen et al., 2004 [triangle]).

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903147X/br2113sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903147X/br2113Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the ICDD for financial support (grant No. 03–02).

supplementary crystallographic information

Comment

Chemistry of caesium phosphates shows a great diversity due to its structural flexibility in adopting different coordination environment. In metal phosphates caesium resides generally in complex polyhedron with up to fourteen vertices providing formation of two- and three-dimensional frameworks. Depending on crystal structure caesium is believed to occupy big cavities and tunnels adapting their geometry. For instance, the structure of Cs3Mo8O11(PO4)8 (Borel et al., 2000) represents two types of irregular surrounding with nine and ten oxygen coordination, Cs2Ti(VO2)3(PO4)3 (Yakubovich et al.,2006) - twelve and fourteen. Herein, the structure of K2Bi(PO4)(WO4) (Zatovsky et al., 2006) represents an interesting host for substitution of potassium atoms by caesium ones, that leads to formation of the first example of caesium-containing phosphate-tungstate Cs2Bi(PO4)(WO4) (Fig 1). Three-dimensional framework of the title compound is organized by linking together [Bi(PO4)(WO4)] nets which are formed by adhesion [BiPO4] layers and WO4 tetrahedra above and below of those layers (Fig. 2). Both phosphate and tungstate tetrahedra have almost regular geometry with typical bond lengths. Caesium atom resides in interlayer space having eightfold coordination duplicating potassium ones' environment in the structure of K2Bi(PO4)(WO4) (Zatovsky et al., 2006). Due to bigger ionic radius of Cs, the distance between two successive nets (a half of a cell dimension a) is 10.657 Å, while for K-analogue is 9.862 Å.

Experimental

Single crystals of the title compound were obtained during investigation in the pseudo-quaternary molten system Cs2O—Bi2O3—P2O5—WO3. A mixture of CsPO3 (1.060 g), Cs2W2O7 (3.725 g) and Bi2O3 (0.840 g) were mixed in an agate mortar, and heated in a platinum crucible up to 1223 K to obtain a homogeneous melt. It was held at this temperature for an hour and cooled down with a rate of 40 K h-1 to 833 K. Crystalline product was leached out from the solidified melt with hot water.

Refinement

Convergence factors (R, wR) and Rint are high due to low intensity of the reflections which is connected with poor quality of crystals. Experiments were carried out for several crystals from different synthetic points, unfortunately, better results than is presented were not found. Taking into account the previous structures isotypic to titled compound there is no doubts in structure determination.

The highest peak and the deepest hole in the final difference map are located at 0.77Å from P1 (2.173 e/Å3) and 0.70Å from P2 (-2.633 e/Å3) respectively.

Figures

Fig. 1.
View of the title compound with displacement ellipsoids at the 50% probability level.
Fig. 2.
View of Cs2Bi(PO4)(WO4).

Crystal data

Cs2Bi(PO4)(WO4)F(000) = 2768
Mr = 817.61Dx = 5.648 Mg m3
Orthorhombic, IbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2b 2cCell parameters from 10697 reflections
a = 21.3144 (10) Åθ = 3.2–30.0°
b = 12.6352 (5) ŵ = 37.87 mm1
c = 7.1412 (3) ÅT = 293 K
V = 1923.21 (14) Å3Prism, colourless
Z = 80.08 × 0.07 × 0.05 mm

Data collection

Oxford Diffraction XCalibur-3 diffractometer1396 independent reflections
Radiation source: fine-focus sealed tube1227 reflections with I > 2σ(I)
graphiteRint = 0.156
[var phi] and ω scansθmax = 30.0°, θmin = 3.2°
Absorption correction: multi-scan (Blessing, 1995)h = −27→29
Tmin = 0.061, Tmax = 0.174k = −17→17
10697 measured reflectionsl = −10→10

Refinement

Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.052Secondary atom site location: difference Fourier map
wR(F2) = 0.115w = 1/[σ2(Fo2) + (0.0396P)2 + 22.3992P] where P = (Fo2 + 2Fc2)/3
S = 1.21(Δ/σ)max < 0.001
1396 reflectionsΔρmax = 2.17 e Å3
61 parametersΔρmin = −2.63 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Bi10.250.58662 (4)00.01381 (17)
Cs10.09029 (3)0.83471 (6)0.21999 (11)0.0233 (2)
W10.09279 (3)0.50.250.01566 (18)
P10.250.8232 (3)00.0081 (6)
O10.2413 (4)0.8984 (6)0.1675 (11)0.0204 (17)
O20.3072 (4)0.7487 (6)0.0220 (11)0.0173 (15)
O30.1403 (4)0.5328 (8)0.0513 (13)0.0258 (18)
O40.0440 (4)0.3925 (8)0.1847 (13)0.031 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Bi10.0116 (3)0.0135 (3)0.0162 (3)0−0.00033 (18)0
Cs10.0166 (4)0.0290 (4)0.0243 (4)0.0014 (3)−0.0003 (2)0.0005 (3)
W10.0107 (3)0.0162 (3)0.0201 (3)000.0007 (2)
P10.0077 (15)0.0086 (13)0.0080 (15)0−0.0014 (10)0
O10.034 (5)0.015 (3)0.012 (4)−0.004 (3)0.002 (3)−0.003 (3)
O20.013 (4)0.017 (3)0.021 (4)−0.001 (3)0.000 (3)0.003 (3)
O30.013 (4)0.036 (5)0.028 (4)−0.007 (4)−0.004 (3)0.006 (4)
O40.020 (5)0.032 (5)0.040 (5)−0.013 (4)0.007 (4)−0.013 (4)

Geometric parameters (Å, °)

Bi1—O22.388 (8)Cs1—O4viii3.111 (10)
Bi1—O2i2.388 (8)Cs1—O4ix3.140 (9)
Bi1—O1ii2.389 (8)Cs1—O13.338 (9)
Bi1—O1iii2.389 (8)Cs1—O3ix3.339 (9)
Bi1—O3i2.463 (8)W1—O41.774 (9)
Bi1—O32.463 (8)W1—O4viii1.774 (9)
Bi1—O1iv2.669 (8)W1—O3viii1.792 (9)
Bi1—O1v2.669 (8)W1—O31.792 (9)
Cs1—O2i2.990 (8)P1—O11.539 (8)
Cs1—O4vi3.031 (9)P1—O1i1.539 (8)
Cs1—O2ii3.046 (8)P1—O2i1.549 (8)
Cs1—O3vii3.088 (9)P1—O21.549 (8)
?—?—??

Symmetry codes: (i) −x+1/2, y, −z; (ii) −x+1/2, −y+3/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x, y−1/2, −z; (v) −x+1/2, y−1/2, z; (vi) −x, y+1/2, −z+1/2; (vii) x, −y+3/2, z+1/2; (viii) x, −y+1, −z+1/2; (ix) x, y+1/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BR2113).

References

  • Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst.37, 335–338.
  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Borel, M. M., Leclaire, A., Chardon, J. & Raveau, B. (2000). Int. J. Inorg. Mater.2, 11–19.
  • Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Abingdon, England.
  • Sheldrick, G. M. (2008). Acta Cryst A64, 112–122. [PubMed]
  • Terebilenko, K. V., Zatovsky, I. V., Baumer, V. N., Slobodyanik, N. S. & Shishkin, O. V. (2008). Acta Cryst. E64, i75. [PMC free article] [PubMed]
  • Yakubovich, O. V., Massa, W. & Dimitrova, O. V. (2006). Solid State Sci.8, 71–76.
  • Zatovsky, I. V., Terebilenko, K. V., Slobodyanik, N. S., Baumer, V. N. & Shishkin, O. V. (2006). Acta Cryst. E62, i193–i195.

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