Single crystals of caesium tantalate(V), Cs10Ta29.27O78, were obtained as a serendipitous product in a welded tantalum ampoule by a blank reaction of CsBr and bis­muth subnitrate [Bi5O(OH)9(NO3)4] with the container material. The crystal structure of the title compound is made up of a three-dimensional framework constituted by two types of layers, viz. (Ta6O15)n and (Ta3O9)n, parallel to (001), which are linked together by TaO6 octa­hedra (3m. symmetry) along [001]. This framework has cavities where three independent Cs+ ions (3m. and 
               m2 symmetry, respectively) are located. The compound reveals a Ta deficiency at one trigonal prismatic coordinated site (
               m2 symmetry). The composition of the title compound was verified by energy-dispersive X-ray analysis of single crystals

Alexander Hofer

Boulay

Haddad

Magnéli

Marini

Martin Zeuner

Michel

Serafin

Sheldrick

Wolfgang Schnick

English

PubMed

Single crystals of caesium tantalate(V), Cs10Ta29.27O78, were obtained as a serendipitous product in a welded tantalum ampoule by a blank reaction of CsBr and bismuth subnitrate [Bi5O(OH)9(NO3)4] with the container material. The crystal structure of the title compound is made up of a three-dimensional framework constituted by two types of layers, viz. (Ta6O15)n and (Ta3O9)n, parallel to (001), which are linked together by TaO6 octahedra (3m. symmetry) along [001]. This framework has cavities where three independent Cs+ ions (3m. and 6m2 symmetry, respectively) are located. The compound reveals a Ta deficiency at one trigonal prismatic coordinated site (6m2 symmetry). The composition of the title compound was verified by energy-dispersive X-ray analysis of single crystals

Zeuner, Martin

Hofer, Alexander

Schnick, Wolfgang

Universität München: Elektronischen Publikationen

Cs10Ta29.27O78
Martin Zeuner, Alexander Hofer and Wolfgang Schnick*
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München,
Lehrstuhl für Anorganische Festkörperchemie, Butenandtstrasse 5–13, D-81377
München, Germany
Correspondence e-mail: wolfgang.schnick@uni-muenchen.de
Received 13 January 2009; accepted 23 January 2009
Key indicators: single-crystal X-ray study; T = 294 K; mean (Ta–O) = 0.010 Å;
disorder in main residue; R factor = 0.033; wR factor = 0.083; data-to-parameter
ratio = 12.8.
Single crystals of caesium tantalate(V), Cs10Ta29.27O78, were
obtained as a serendipitous product in a welded tantalum
ampoule by a blank reaction of CsBr and bismuth subnitrate
[Bi5O(OH)9(NO3)4] with the container material. The crystal
structure of the title compound is made up of a three-
dimensional framework constituted by two types of layers, viz.
(Ta6O15)n and (Ta3O9)n, parallel to (001), which are linked
together by TaO6 octahedra (3m. symmetry) along [001]. This
framework has cavities where three independent Cs+ ions (3m.
and 6m2 symmetry, respectively) are located. The compound
reveals a Ta deficiency at one trigonal prismatic coordinated
site (6m2 symmetry). The composition of the title compound
was verified by energy-dispersive X-ray analysis of single
crystals.
Related literature
For a previous powder diffraction study of Cs10Ta29.27O78, see:
Michel et al. (1978). For an isotypic compound, see: Haddad &
Jouini (1997). For general background and related structures,
see: du Boulay et al. (2003); Magnéli (1953); Marini et al.
(1979); Serafin & Hoppe (1982).
Experimental
Crystal data
Cs10Ta29.27O78
Mr = 7873.51
Hexagonal, P63=mmc
a = 7.5170 (11) Å
c = 36.340 (7) Å
V = 1778.3 (5) Å3
Z = 1
Mo K radiation
 = 49.96 mm1
T = 294 (2) K
0.03  0.02  0.01 mm
Data collection
Stoe IPDS-I diffractometer
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1999)
Tmin = 0.218, Tmax = 0.607
14043 measured reflections
855 independent reflections
587 reflections with I > 2(I)
Rint = 0.119
Refinement
R[F 2 > 2(F 2)] = 0.033
wR(F 2) = 0.083
S = 0.89
855 reflections
67 parameters
max = 1.54 e Å
3
min = 3.28 e Å
3
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-
AREA; data reduction: X-AREA; program(s) used to solve structure:
SHELXS97 (Sheldrick, 2008); program(s) used to refine structure:
SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND
(Brandenburg, 1999); software used to prepare material for publi-
cation: SHELXL97.
The authors are indebted to Thomas Miller for performing
the single-crystal X-ray diffractometry. Financial support by
the Fonds der Chemischen Industrie is gratefully acknowl-
edged.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: WM2217).
References
Boulay, D. du, Oono, A. & Ishizawa, N. (2003). Acta Cryst. E59, i86–i88.
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Haddad, A. & Jouini, T. (1997). J. Solid State Chem. 25, 251–261.
Magnéli, A. (1953). Acta Chem. Scand. 7, 315–324.
Marini, A., Michel, C. & Raveau, B. (1979). J. Rev. Chim. Miner. 16, 73–79.
Michel, C., Guyomarch, A. & Raveau, B. (1978). J. Solid State Chem. 25, 251–
261.
Serafin, M. & Hoppe, R. (1982). Z. Anorg. Allg. Chem. 493, 77–92.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Stoe & Cie (1999). X-SHAPE. Stoe & Cie, Darmstadt, Germany.
Stoe & Cie (2002). X-AREA. Stoe & Cie, Darmstadt, Germany.
inorganic compounds
i12 Zeuner et al. doi:10.1107/S1600536809002967 Acta Cryst. (2009). E65, i12
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
supplementary materials
supplementary materials
sup-1
Acta Cryst. (2009). E65, i12    [ doi:10.1107/S1600536809002967 ]
Cs10Ta29.27O78
M. Zeuner, A. Hofer and W. Schnick
Comment
The title compound has a three-dimensional framework, constituted by two types of layers, (Ta6O15)n (Fig. 1, green) and
(Ta3O9)n (Fig. 2, blue), parallel to (001). These layers are linked together along [001], according to the sequence (Ta6O15)n-
TaO6-(Ta3O9)n-(Ta3O9)n-TaO6, by sharing corners of TaO6 octahedra (red, Fig. 3). The tantalum atom with deficient oc-
cupation is located in a site with trigonal-prismatic coordinated sites (yellow), between two Ta3O9 units belonging to two
neighboring (Ta3O9)n layers. This framework has cavities which communicate with interconnected channels, parallel to
[100]. Cs+ ions (black) are located in these cavities. Geometric parameters of the title compound are in the usual ranges.
Based on a previous powder diffraction study of Cs10Ta29.27O78 reported by Michel et al. (1978), an additional Ta site was
found, but was not observed in the current re-investigation. The closely related structure of Tl10Nb29.2O78 was also reported
(Marini et al., 1979) with an additional Nb site with too short interatomic distances between the Nb atoms.
The title compound crystallizes isotypically with Rb5VONb14O38 (Haddad & Jouini, 1997), in which the vanadium atom
occupies the trigonal-prismatic Ta deficiency site of the title compound. The related compound Cs3Ta5O14 was first invest-
igated by powder diffraction studies by Serafin & Hoppe (1982) and was later re-investigated on the basis of single-crystal
X-ray diffraction by du Boulay et al. (2003). An overview on the related hexagonal tungsten bronzes of potassium, rubidium
and caesium was presented by Magnéli (1953).
Experimental
The title compound was obtained as a serendipitious product by the reaction of CsBr and bismuth subnitrate
(Bi5O(OH)9(NO3)4, 98%, Sigma-Aldrich) with the tantalum container material. It was synthesized under argon at temper-
atures of 1523 K in a welded tantalum ampoule. The air stable title compound crystallizes in brown rods. The chemical
composition of the single-crystal was confirmed by energy-dispersive X-ray (EDX) analysis which revealed no impurity
elements.
Refinement
The site occupation factor (s.o.f.) of the Ta-deficient Ta4 site was refined freely. The maximum residual electron density
lies 0.95 Å from O1 and the minimum residual electron density lies at the position of the Cs1 atom.
supplementary materials
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Figures
Fig. 1. View along [001] on the (Ta6O15)n layer.
Fig. 2. View along [001] on the (Ta3O9)n layer.
Fig. 3. View along [010] on the layers of the title compound connected via TaO6 octahedra.
Displacement ellipsoids are drawn at the 50% probability level.
caesium tantalate(V)
Crystal data
Cs10Ta29.27O78 Z = 1
Mr = 7873.51 F000 = 3310.4
Hexagonal, P63/mmc Dx = 7.352 Mg m−3
Hall symbol: -P 6c 2c Mo Kα radiationλ = 0.71073 Å
a = 7.5170 (11) Å Cell parameters from 1275 reflections
b = 7.5170 (11) Å θ = 2.6–31.6º
c = 36.340 (7) Å µ = 49.96 mm−1
α = 90º T = 294 (2) K
β = 90º Rod, brown
γ = 120º 0.03 × 0.02 × 0.01 mm
V = 1778.3 (5) Å3
Data collection
Stoe IPDS-I 855 independent reflections
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diffractometer
Radiation source: fine-focus sealed tube 587 reflections with I > 2σ(I)
Monochromator: graphite Rint = 0.119
T = 294(2) K θmax = 27.5º
ω scans θmin = 3.1º
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1999) h = −9→9
Tmin = 0.218, Tmax = 0.607 k = −9→9
14043 measured reflections l = −46→46
Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Least-squares matrix: full Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033
  w = 1/[σ2(Fo2) + (0.0516P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.083 (Δ/σ)max < 0.001
S = 0.89 Δρmax = 1.54 e Å−3
855 reflections Δρmin = −3.28 e Å−3
67 parameters Extinction correction: none
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 mat-
rix. 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, convention-
al 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)
x y z Uiso*/Ueq Occ. (<1)
Ta1 0.0000 0.0000 0.11749 (3) 0.0166 (2)
Ta2 0.33551 (10) 0.16775 (5) 0.034126 (15) 0.01525 (19)
Ta3 0.17146 (6) 0.34292 (11) 0.196383 (17) 0.0204 (2)
Ta4 0.0000 0.0000 0.2500 0.0163 (8) 0.633 (10)
O1 0.0814 (19) 0.5407 (9) 0.1881 (4) 0.021 (2)
O2 0.5486 (9) 0.4514 (9) 0.0368 (3) 0.019 (2)
O3 0.1256 (9) 0.2511 (18) 0.1456 (3) 0.022 (2)
O4 0.2470 (17) 0.1235 (8) 0.0825 (3) 0.017 (2)
O5 0.1410 (8) −0.1410 (8) 0.0233 (3) 0.012 (2)
O6 0.2379 (18) 0.1190 (9) 0.2082 (3) 0.019 (2)
O7 0.1878 (15) 0.376 (3) 0.2500 0.023 (4)
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Cs1 0.6667 0.3333 0.2500 0.0337 (6)
Cs2 0.3333 0.6667 0.08755 (7) 0.0459 (6)
Cs3 0.6667 0.3333 0.13681 (8) 0.0564 (7)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Ta1 0.0158 (3) 0.0158 (3) 0.0180 (5) 0.00791 (16) 0.000 0.000
Ta2 0.0141 (3) 0.0144 (3) 0.0173 (3) 0.00703 (15) −0.0001 (2) −0.00005 (11)
Ta3 0.0181 (3) 0.0217 (4) 0.0226 (4) 0.01083 (19) −0.00299 (13) −0.0060 (3)
Ta4 0.0151 (10) 0.0151 (10) 0.0188 (13) 0.0075 (5) 0.000 0.000
O1 0.019 (5) 0.014 (4) 0.031 (6) 0.010 (3) −0.001 (5) 0.000 (2)
O2 0.020 (4) 0.020 (4) 0.022 (5) 0.013 (5) 0.002 (2) −0.002 (2)
O3 0.025 (5) 0.019 (6) 0.020 (5) 0.010 (3) 0.000 (2) 0.000 (4)
O4 0.016 (5) 0.016 (4) 0.019 (5) 0.008 (3) 0.007 (4) 0.004 (2)
O5 0.015 (4) 0.015 (4) 0.002 (4) 0.005 (4) −0.0019 (19) 0.0019 (19)
O6 0.016 (5) 0.013 (4) 0.028 (6) 0.008 (3) 0.000 (4) 0.000 (2)
O7 0.021 (6) 0.038 (11) 0.015 (7) 0.019 (5) 0.000 0.000
Cs1 0.0317 (9) 0.0317 (9) 0.0377 (15) 0.0159 (5) 0.000 0.000
Cs2 0.0443 (8) 0.0443 (8) 0.0493 (15) 0.0221 (4) 0.000 0.000
Cs3 0.0626 (11) 0.0626 (11) 0.0441 (14) 0.0313 (6) 0.000 0.000
Geometric parameters (Å, °)
Ta1—O3 1.928 (12) Ta3—O7 1.960 (2)
Ta1—O3i 1.928 (12) Ta3—O6ii 2.028 (12)
Ta1—O3ii 1.928 (12) Ta3—O6 2.027 (10)
Ta1—O4i 2.050 (11) Ta3—Ta4 2.9631 (8)
Ta1—O4ii 2.050 (11) Ta4—O6i 2.170 (12)
Ta1—O4 2.050 (11) Ta4—O6ii 2.170 (12)
Ta2—O4 1.850 (11) Ta4—O6vii 2.170 (12)
Ta2—O2 1.925 (7) Ta4—O6 2.170 (12)
Ta2—O2iii 1.925 (8) Ta4—O6viii 2.170 (12)
Ta2—O5ii 2.070 (4) Ta4—O6ix 2.170 (12)
Ta2—O5 2.070 (4) Ta4—O7ii 2.45 (2)
Ta2—O5iv 2.114 (10) Ta4—O7 2.45 (2)
Ta2—Ta2v 3.3049 (10) Ta4—O7ix 2.446 (19)
Ta2—Ta2iv 3.3049 (10) Ta4—Ta3ii 2.9631 (8)
Ta3—O3 1.940 (12) Ta4—Ta3i 2.9631 (8)
Ta3—O1 1.941 (12) Ta4—Ta3vii 2.9631 (8)
Ta3—O1vi 1.941 (12)
O3—Ta1—O3i 94.5 (5) O3—Ta3—Ta4 113.2 (4)
O3—Ta1—O3ii 94.5 (5) O1—Ta3—Ta4 127.0 (4)
O3i—Ta1—O3ii 94.5 (5) O1vi—Ta3—Ta4 127.0 (4)
O3—Ta1—O4i 173.7 (5) O7—Ta3—Ta4 55.1 (6)
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O3i—Ta1—O4i 89.8 (3) O6ii—Ta3—Ta4 47.1 (3)
O3ii—Ta1—O4i 89.8 (3) O6—Ta3—Ta4 47.1 (3)
O3—Ta1—O4ii 89.8 (3) O6i—Ta4—O6ii 76.4 (5)
O3i—Ta1—O4ii 173.7 (5) O6i—Ta4—O6vii 138.2 (2)
O3ii—Ta1—O4ii 89.8 (3) O6ii—Ta4—O6vii 138.2 (2)
O4i—Ta1—O4ii 85.6 (5) O6i—Ta4—O6 76.4 (5)
O3—Ta1—O4 89.8 (3) O6ii—Ta4—O6 76.4 (5)
O3i—Ta1—O4 89.8 (3) O6vii—Ta4—O6 88.9 (6)
O3ii—Ta1—O4 173.7 (5) O6i—Ta4—O6viii 138.2 (2)
O4i—Ta1—O4 85.6 (5) O6ii—Ta4—O6viii 88.9 (6)
O4ii—Ta1—O4 85.6 (5) O6vii—Ta4—O6viii 76.4 (5)
O4—Ta2—O2 100.2 (4) O6—Ta4—O6viii 138.2 (2)
O4—Ta2—O2iii 100.2 (4) O6i—Ta4—O6ix 88.9 (6)
O2—Ta2—O2iii 87.5 (7) O6ii—Ta4—O6ix 138.2 (2)
O4—Ta2—O5ii 89.5 (4) O6vii—Ta4—O6ix 76.4 (5)
O2—Ta2—O5ii 85.4 (4) O6—Ta4—O6ix 138.2 (2)
O2iii—Ta2—O5ii 168.9 (4) O6viii—Ta4—O6ix 76.4 (5)
O4—Ta2—O5 89.5 (4) O6i—Ta4—O7ii 69.09 (12)
O2—Ta2—O5 168.9 (4) O6ii—Ta4—O7ii 69.09 (12)
O2iii—Ta2—O5 85.4 (4) O6vii—Ta4—O7ii 135.5 (3)
O5ii—Ta2—O5 100.3 (6) O6—Ta4—O7ii 135.5 (3)
O4—Ta2—O5iv 152.4 (5) O6viii—Ta4—O7ii 69.09 (12)
O2—Ta2—O5iv 99.7 (4) O6ix—Ta4—O7ii 69.09 (12)
O2iii—Ta2—O5iv 99.7 (4) O6i—Ta4—O7 135.5 (3)
O5ii—Ta2—O5iv 73.2 (4) O6ii—Ta4—O7 69.09 (12)
O5—Ta2—O5iv 73.2 (4) O6vii—Ta4—O7 69.09 (12)
O4—Ta2—Ta2v 127.6 (2) O6—Ta4—O7 69.09 (12)
O2—Ta2—Ta2v 132.2 (3) O6viii—Ta4—O7 69.09 (12)
O2iii—Ta2—Ta2v 83.1 (3) O6ix—Ta4—O7 135.5 (3)
O5ii—Ta2—Ta2v 95.4 (3) O7ii—Ta4—O7 120.000 (1)
O5—Ta2—Ta2v 38.3 (3) O6i—Ta4—O7ix 69.09 (12)
O5iv—Ta2—Ta2v 37.37 (10) O6ii—Ta4—O7ix 135.5 (3)
O4—Ta2—Ta2iv 127.6 (2) O6vii—Ta4—O7ix 69.09 (12)
O2—Ta2—Ta2iv 83.1 (3) O6—Ta4—O7ix 69.09 (12)
O2iii—Ta2—Ta2iv 132.2 (3) O6viii—Ta4—O7ix 135.5 (3)
O5ii—Ta2—Ta2iv 38.3 (3) O6ix—Ta4—O7ix 69.09 (12)
O5—Ta2—Ta2iv 95.4 (3) O7ii—Ta4—O7ix 120.000 (1)
O5iv—Ta2—Ta2iv 37.37 (10) O7—Ta4—O7ix 120.000 (2)
Ta2v—Ta2—Ta2iv 69.83 (3) Ta3ii—Ta4—Ta3vii 135.741 (10)
O3—Ta3—O1 93.3 (4) Ta3i—Ta4—Ta3vii 135.741 (10)
O3—Ta3—O1vi 93.3 (5) Ta3—O1—Ta3x 140.3 (7)
supplementary materials
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O1—Ta3—O1vi 94.1 (7) Ta2—O2—Ta2xi 151.8 (7)
O3—Ta3—O7 168.3 (7) Ta1—O3—Ta3 139.9 (7)
O1—Ta3—O7 94.7 (5) Ta2—O4—Ta1 146.5 (7)
O1vi—Ta3—O7 94.7 (5) Ta2i—O5—Ta2 132.0 (6)
O3—Ta3—O6ii 88.8 (4) Ta2i—O5—Ta2v 104.3 (3)
O1—Ta3—O6ii 91.5 (5) Ta2—O5—Ta2v 104.3 (3)
O1vi—Ta3—O6ii 173.9 (5) Ta3i—O6—Ta3 145.0 (6)
O7—Ta3—O6ii 82.4 (6) Ta3i—O6—Ta4 89.8 (3)
O3—Ta3—O6 88.8 (4) Ta3—O6—Ta4 89.8 (3)
O1—Ta3—O6 173.9 (5) Ta3—O7—Ta3vii 167.5 (11)
O1vi—Ta3—O6 91.5 (5) Ta3—O7—Ta4 83.8 (6)
O7—Ta3—O6 82.4 (5) Ta3vii—O7—Ta4 83.8 (6)
O6ii—Ta3—O6 82.9 (6)
Symmetry codes: (i) −x+y, −x, z; (ii) −y, x−y, z; (iii) −y+1, x−y, z; (iv) x−y, x, −z; (v) y, −x+y, −z; (vi) −y+1, x−y+1, z; (vii) x, y, −z+1/2;
(viii) −y, x−y, −z+1/2; (ix) −x+y, −x, −z+1/2; (x) −x+y, −x+1, z; (xi) −x+y+1, −x+1, z.
supplementary materials
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Fig. 1
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Fig. 2
supplementary materials
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Fig. 3


Cs10Ta29.27O78

Single crystals of caesium tantalate(V), Cs10Ta29.27O78, were obtained as a serendipitous product in a welded tantalum ampoule by a blank reaction of CsBr and bismuth subnitrate [Bi5O(OH)9(NO3)4] with the container material. The crystal structure of the title compound is made up of a three-dimensional framework constituted by two types of layers, viz. (Ta6O15)n and (Ta3O9)n, parallel to (001), which are linked together by TaO6 octahedra (3m. symmetry) along [001]. This framework has cavities where three independent Cs+ ions (3m. and overline{6}m2 symmetry, respectively) are located. The compound reveals a Ta deficiency at one trigonal prismatic coordinated site (overline{6}m2 symmetry). The composition of the title compound was verified by energy-dispersive X-ray analysis of single crystals

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Cs10Ta29.27O78Martin Zeuner, Alexander Hofer and Wolfgang Schnick*Department Chemie und Biochemie, Ludwig-Maximilians-Universita¨t Mu¨nchen,Lehrstuhl fu¨r Anorganische Festko¨rperchemie, Butenandtstrasse 5–13, D-81377Mu¨nchen, GermanyCorrespondence e-mail: wolfgang.schnick@uni-muenchen.deReceived 13 January 2009; accepted 23 January 2009Key indicators: single-crystal X-ray study; T = 294 K; mean (Ta–O) = 0.010 A˚;disorder in main residue; R factor = 0.033; wR factor = 0.083; data-to-parameterratio = 12.8.Single crystals of caesium tantalate(V), Cs10Ta29.27O78, wereobtained as a serendipitous product in a welded tantalumampoule by a blank reaction of CsBr and bismuth subnitrate[Bi5O(OH)9(NO3)4] with the container material. The crystalstructure of the title compound is made up of a three-dimensional framework constituted by two types of layers, viz.(Ta6O15)n and (Ta3O9)n, parallel to (001), which are linkedtogether by TaO6 octahedra (3m. symmetry) along [001]. Thisframework has cavities where three independent Cs+ ions (3m.and 6m2 symmetry, respectively) are located. The compoundreveals a Ta deficiency at one trigonal prismatic coordinatedsite (6m2 symmetry). The composition of the title compoundwas verified by energy-dispersive X-ray analysis of singlecrystals.Related literatureFor a previous powder diffraction study of Cs10Ta29.27O78, see:Michel et al. (1978). For an isotypic compound, see: Haddad &Jouini (1997). For general background and related structures,see: du Boulay et al. (2003); Magne´li (1953); Marini et al.(1979); Serafin & Hoppe (1982).ExperimentalCrystal dataCs10Ta29.27O78Mr = 7873.51Hexagonal, P63=mmca = 7.5170 (11) A˚c = 36.340 (7) A˚V = 1778.3 (5) A˚3Z = 1Mo K radiation = 49.96 mm1T = 294 (2) K0.03  0.02  0.01 mmData collectionStoe IPDS-I diffractometerAbsorption correction: numerical(X-SHAPE; Stoe & Cie, 1999)Tmin = 0.218, Tmax = 0.60714043 measured reflections855 independent reflections587 reflections with I > 2(I)Rint = 0.119RefinementR[F 2 > 2(F 2)] = 0.033wR(F 2) = 0.083S = 0.89855 reflections67 parametersmax = 1.54 e A˚3min = 3.28 e A˚3Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure:SHELXS97 (Sheldrick, 2008); program(s) used to refine structure:SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND(Brandenburg, 1999); software used to prepare material for publi-cation: SHELXL97.The authors are indebted to Thomas Miller for performingthe single-crystal X-ray diffractometry. Financial support bythe Fonds der Chemischen Industrie is gratefully acknowl-edged.Supplementary data and figures for this paper are available from theIUCr electronic archives (Reference: WM2217).ReferencesBoulay, D. du, Oono, A. & Ishizawa, N. (2003). Acta Cryst. E59, i86–i88.Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.Haddad, A. & Jouini, T. (1997). J. Solid State Chem. 25, 251–261.Magne´li, A. (1953). Acta Chem. Scand. 7, 315–324.Marini, A., Michel, C. & Raveau, B. (1979). J. Rev. Chim. Miner. 16, 73–79.Michel, C., Guyomarch, A. & Raveau, B. (1978). J. Solid State Chem. 25, 251–261.Serafin, M. & Hoppe, R. (1982). Z. Anorg. Allg. Chem. 493, 77–92.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Stoe & Cie (1999). X-SHAPE. Stoe & Cie, Darmstadt, Germany.Stoe & Cie (2002). X-AREA. Stoe & Cie, Darmstadt, Germany.inorganic compoundsi12 Zeuner et al. doi:10.1107/S1600536809002967 Acta Cryst. (2009). E65, i12Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssupplementary materialssup-1Acta Cryst. (2009). E65, i12    [ doi:10.1107/S1600536809002967 ]Cs10Ta29.27O78M. Zeuner, A. Hofer and W. SchnickCommentThe title compound has a three-dimensional framework, constituted by two types of layers, (Ta6O15)n (Fig. 1, green) and(Ta3O9)n (Fig. 2, blue), parallel to (001). These layers are linked together along [001], according to the sequence (Ta6O15)n-TaO6-(Ta3O9)n-(Ta3O9)n-TaO6, by sharing corners of TaO6 octahedra (red, Fig. 3). The tantalum atom with deficient oc-cupation is located in a site with trigonal-prismatic coordinated sites (yellow), between two Ta3O9 units belonging to twoneighboring (Ta3O9)n layers. This framework has cavities which communicate with interconnected channels, parallel to[100]. Cs+ ions (black) are located in these cavities. Geometric parameters of the title compound are in the usual ranges.Based on a previous powder diffraction study of Cs10Ta29.27O78 reported by Michel et al. (1978), an additional Ta site wasfound, but was not observed in the current re-investigation. The closely related structure of Tl10Nb29.2O78 was also reported(Marini et al., 1979) with an additional Nb site with too short interatomic distances between the Nb atoms.The title compound crystallizes isotypically with Rb5VONb14O38 (Haddad & Jouini, 1997), in which the vanadium atomoccupies the trigonal-prismatic Ta deficiency site of the title compound. The related compound Cs3Ta5O14 was first invest-igated by powder diffraction studies by Serafin & Hoppe (1982) and was later re-investigated on the basis of single-crystalX-ray diffraction by du Boulay et al. (2003). An overview on the related hexagonal tungsten bronzes of potassium, rubidiumand caesium was presented by Magnéli (1953).ExperimentalThe title compound was obtained as a serendipitious product by the reaction of CsBr and bismuth subnitrate(Bi5O(OH)9(NO3)4, 98%, Sigma-Aldrich) with the tantalum container material. It was synthesized under argon at temper-atures of 1523 K in a welded tantalum ampoule. The air stable title compound crystallizes in brown rods. The chemicalcomposition of the single-crystal was confirmed by energy-dispersive X-ray (EDX) analysis which revealed no impurityelements.RefinementThe site occupation factor (s.o.f.) of the Ta-deficient Ta4 site was refined freely. The maximum residual electron densitylies 0.95 Å from O1 and the minimum residual electron density lies at the position of the Cs1 atom.supplementary materialssup-2FiguresFig. 1. View along [001] on the (Ta6O15)n layer.Fig. 2. View along [001] on the (Ta3O9)n layer.Fig. 3. View along [010] on the layers of the title compound connected via TaO6 octahedra.Displacement ellipsoids are drawn at the 50% probability level.caesium tantalate(V)Crystal dataCs10Ta29.27O78 Z = 1Mr = 7873.51 F000 = 3310.4Hexagonal, P63/mmc Dx = 7.352 Mg m−3Hall symbol: -P 6c 2c Mo Kα radiationλ = 0.71073 Åa = 7.5170 (11) Å Cell parameters from 1275 reflectionsb = 7.5170 (11) Å θ = 2.6–31.6ºc = 36.340 (7) Å µ = 49.96 mm−1α = 90º T = 294 (2) Kβ = 90º Rod, brownγ = 120º 0.03 × 0.02 × 0.01 mmV = 1778.3 (5) Å3Data collectionStoe IPDS-I 855 independent reflectionssupplementary materialssup-3diffractometerRadiation source: fine-focus sealed tube 587 reflections with I > 2σ(I)Monochromator: graphite Rint = 0.119T = 294(2) K θmax = 27.5ºω scans θmin = 3.1ºAbsorption correction: numerical(X-SHAPE; Stoe & Cie, 1999) h = −9→9Tmin = 0.218, Tmax = 0.607 k = −9→914043 measured reflections l = −46→46RefinementRefinement on F2Primary atom site location: structure-invariant directmethodsLeast-squares matrix: full Secondary atom site location: difference Fourier mapR[F2 > 2σ(F2)] = 0.033  w = 1/[σ2(Fo2) + (0.0516P)2]where P = (Fo2 + 2Fc2)/3wR(F2) = 0.083 (Δ/σ)max < 0.001S = 0.89 Δρmax = 1.54 e Å−3855 reflections Δρmin = −3.28 e Å−367 parameters Extinction correction: noneSpecial detailsGeometry. 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 mat-rix. 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; correlationsbetween e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment ofcell 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, convention-al 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 largeas 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)x y z Uiso*/Ueq Occ. (<1)Ta1 0.0000 0.0000 0.11749 (3) 0.0166 (2)Ta2 0.33551 (10) 0.16775 (5) 0.034126 (15) 0.01525 (19)Ta3 0.17146 (6) 0.34292 (11) 0.196383 (17) 0.0204 (2)Ta4 0.0000 0.0000 0.2500 0.0163 (8) 0.633 (10)O1 0.0814 (19) 0.5407 (9) 0.1881 (4) 0.021 (2)O2 0.5486 (9) 0.4514 (9) 0.0368 (3) 0.019 (2)O3 0.1256 (9) 0.2511 (18) 0.1456 (3) 0.022 (2)O4 0.2470 (17) 0.1235 (8) 0.0825 (3) 0.017 (2)O5 0.1410 (8) −0.1410 (8) 0.0233 (3) 0.012 (2)O6 0.2379 (18) 0.1190 (9) 0.2082 (3) 0.019 (2)O7 0.1878 (15) 0.376 (3) 0.2500 0.023 (4)supplementary materialssup-4Cs1 0.6667 0.3333 0.2500 0.0337 (6)Cs2 0.3333 0.6667 0.08755 (7) 0.0459 (6)Cs3 0.6667 0.3333 0.13681 (8) 0.0564 (7)Atomic displacement parameters (Å2)U11 U22 U33 U12 U13 U23Ta1 0.0158 (3) 0.0158 (3) 0.0180 (5) 0.00791 (16) 0.000 0.000Ta2 0.0141 (3) 0.0144 (3) 0.0173 (3) 0.00703 (15) −0.0001 (2) −0.00005 (11)Ta3 0.0181 (3) 0.0217 (4) 0.0226 (4) 0.01083 (19) −0.00299 (13) −0.0060 (3)Ta4 0.0151 (10) 0.0151 (10) 0.0188 (13) 0.0075 (5) 0.000 0.000O1 0.019 (5) 0.014 (4) 0.031 (6) 0.010 (3) −0.001 (5) 0.000 (2)O2 0.020 (4) 0.020 (4) 0.022 (5) 0.013 (5) 0.002 (2) −0.002 (2)O3 0.025 (5) 0.019 (6) 0.020 (5) 0.010 (3) 0.000 (2) 0.000 (4)O4 0.016 (5) 0.016 (4) 0.019 (5) 0.008 (3) 0.007 (4) 0.004 (2)O5 0.015 (4) 0.015 (4) 0.002 (4) 0.005 (4) −0.0019 (19) 0.0019 (19)O6 0.016 (5) 0.013 (4) 0.028 (6) 0.008 (3) 0.000 (4) 0.000 (2)O7 0.021 (6) 0.038 (11) 0.015 (7) 0.019 (5) 0.000 0.000Cs1 0.0317 (9) 0.0317 (9) 0.0377 (15) 0.0159 (5) 0.000 0.000Cs2 0.0443 (8) 0.0443 (8) 0.0493 (15) 0.0221 (4) 0.000 0.000Cs3 0.0626 (11) 0.0626 (11) 0.0441 (14) 0.0313 (6) 0.000 0.000Geometric parameters (Å, °)Ta1—O3 1.928 (12) Ta3—O7 1.960 (2)Ta1—O3i 1.928 (12) Ta3—O6ii 2.028 (12)Ta1—O3ii 1.928 (12) Ta3—O6 2.027 (10)Ta1—O4i 2.050 (11) Ta3—Ta4 2.9631 (8)Ta1—O4ii 2.050 (11) Ta4—O6i 2.170 (12)Ta1—O4 2.050 (11) Ta4—O6ii 2.170 (12)Ta2—O4 1.850 (11) Ta4—O6vii 2.170 (12)Ta2—O2 1.925 (7) Ta4—O6 2.170 (12)Ta2—O2iii 1.925 (8) Ta4—O6viii 2.170 (12)Ta2—O5ii 2.070 (4) Ta4—O6ix 2.170 (12)Ta2—O5 2.070 (4) Ta4—O7ii 2.45 (2)Ta2—O5iv 2.114 (10) Ta4—O7 2.45 (2)Ta2—Ta2v 3.3049 (10) Ta4—O7ix 2.446 (19)Ta2—Ta2iv 3.3049 (10) Ta4—Ta3ii 2.9631 (8)Ta3—O3 1.940 (12) Ta4—Ta3i 2.9631 (8)Ta3—O1 1.941 (12) Ta4—Ta3vii 2.9631 (8)Ta3—O1vi 1.941 (12)O3—Ta1—O3i 94.5 (5) O3—Ta3—Ta4 113.2 (4)O3—Ta1—O3ii 94.5 (5) O1—Ta3—Ta4 127.0 (4)O3i—Ta1—O3ii 94.5 (5) O1vi—Ta3—Ta4 127.0 (4)O3—Ta1—O4i 173.7 (5) O7—Ta3—Ta4 55.1 (6)supplementary materialssup-5O3i—Ta1—O4i 89.8 (3) O6ii—Ta3—Ta4 47.1 (3)O3ii—Ta1—O4i 89.8 (3) O6—Ta3—Ta4 47.1 (3)O3—Ta1—O4ii 89.8 (3) O6i—Ta4—O6ii 76.4 (5)O3i—Ta1—O4ii 173.7 (5) O6i—Ta4—O6vii 138.2 (2)O3ii—Ta1—O4ii 89.8 (3) O6ii—Ta4—O6vii 138.2 (2)O4i—Ta1—O4ii 85.6 (5) O6i—Ta4—O6 76.4 (5)O3—Ta1—O4 89.8 (3) O6ii—Ta4—O6 76.4 (5)O3i—Ta1—O4 89.8 (3) O6vii—Ta4—O6 88.9 (6)O3ii—Ta1—O4 173.7 (5) O6i—Ta4—O6viii 138.2 (2)O4i—Ta1—O4 85.6 (5) O6ii—Ta4—O6viii 88.9 (6)O4ii—Ta1—O4 85.6 (5) O6vii—Ta4—O6viii 76.4 (5)O4—Ta2—O2 100.2 (4) O6—Ta4—O6viii 138.2 (2)O4—Ta2—O2iii 100.2 (4) O6i—Ta4—O6ix 88.9 (6)O2—Ta2—O2iii 87.5 (7) O6ii—Ta4—O6ix 138.2 (2)O4—Ta2—O5ii 89.5 (4) O6vii—Ta4—O6ix 76.4 (5)O2—Ta2—O5ii 85.4 (4) O6—Ta4—O6ix 138.2 (2)O2iii—Ta2—O5ii 168.9 (4) O6viii—Ta4—O6ix 76.4 (5)O4—Ta2—O5 89.5 (4) O6i—Ta4—O7ii 69.09 (12)O2—Ta2—O5 168.9 (4) O6ii—Ta4—O7ii 69.09 (12)O2iii—Ta2—O5 85.4 (4) O6vii—Ta4—O7ii 135.5 (3)O5ii—Ta2—O5 100.3 (6) O6—Ta4—O7ii 135.5 (3)O4—Ta2—O5iv 152.4 (5) O6viii—Ta4—O7ii 69.09 (12)O2—Ta2—O5iv 99.7 (4) O6ix—Ta4—O7ii 69.09 (12)O2iii—Ta2—O5iv 99.7 (4) O6i—Ta4—O7 135.5 (3)O5ii—Ta2—O5iv 73.2 (4) O6ii—Ta4—O7 69.09 (12)O5—Ta2—O5iv 73.2 (4) O6vii—Ta4—O7 69.09 (12)O4—Ta2—Ta2v 127.6 (2) O6—Ta4—O7 69.09 (12)O2—Ta2—Ta2v 132.2 (3) O6viii—Ta4—O7 69.09 (12)O2iii—Ta2—Ta2v 83.1 (3) O6ix—Ta4—O7 135.5 (3)O5ii—Ta2—Ta2v 95.4 (3) O7ii—Ta4—O7 120.000 (1)O5—Ta2—Ta2v 38.3 (3) O6i—Ta4—O7ix 69.09 (12)O5iv—Ta2—Ta2v 37.37 (10) O6ii—Ta4—O7ix 135.5 (3)O4—Ta2—Ta2iv 127.6 (2) O6vii—Ta4—O7ix 69.09 (12)O2—Ta2—Ta2iv 83.1 (3) O6—Ta4—O7ix 69.09 (12)O2iii—Ta2—Ta2iv 132.2 (3) O6viii—Ta4—O7ix 135.5 (3)O5ii—Ta2—Ta2iv 38.3 (3) O6ix—Ta4—O7ix 69.09 (12)O5—Ta2—Ta2iv 95.4 (3) O7ii—Ta4—O7ix 120.000 (1)O5iv—Ta2—Ta2iv 37.37 (10) O7—Ta4—O7ix 120.000 (2)Ta2v—Ta2—Ta2iv 69.83 (3) Ta3ii—Ta4—Ta3vii 135.741 (10)O3—Ta3—O1 93.3 (4) Ta3i—Ta4—Ta3vii 135.741 (10)O3—Ta3—O1vi 93.3 (5) Ta3—O1—Ta3x 140.3 (7)supplementary materialssup-6O1—Ta3—O1vi 94.1 (7) Ta2—O2—Ta2xi 151.8 (7)O3—Ta3—O7 168.3 (7) Ta1—O3—Ta3 139.9 (7)O1—Ta3—O7 94.7 (5) Ta2—O4—Ta1 146.5 (7)O1vi—Ta3—O7 94.7 (5) Ta2i—O5—Ta2 132.0 (6)O3—Ta3—O6ii 88.8 (4) Ta2i—O5—Ta2v 104.3 (3)O1—Ta3—O6ii 91.5 (5) Ta2—O5—Ta2v 104.3 (3)O1vi—Ta3—O6ii 173.9 (5) Ta3i—O6—Ta3 145.0 (6)O7—Ta3—O6ii 82.4 (6) Ta3i—O6—Ta4 89.8 (3)O3—Ta3—O6 88.8 (4) Ta3—O6—Ta4 89.8 (3)O1—Ta3—O6 173.9 (5) Ta3—O7—Ta3vii 167.5 (11)O1vi—Ta3—O6 91.5 (5) Ta3—O7—Ta4 83.8 (6)O7—Ta3—O6 82.4 (5) Ta3vii—O7—Ta4 83.8 (6)O6ii—Ta3—O6 82.9 (6)Symmetry codes: (i) −x+y, −x, z; (ii) −y, x−y, z; (iii) −y+1, x−y, z; (iv) x−y, x, −z; (v) y, −x+y, −z; (vi) −y+1, x−y+1, z; (vii) x, y, −z+1/2;(viii) −y, x−y, −z+1/2; (ix) −x+y, −x, −z+1/2; (x) −x+y, −x+1, z; (xi) −x+y+1, −x+1, z.supplementary materialssup-7Fig. 1supplementary materialssup-8Fig. 2supplementary materialssup-9Fig. 3

Based on a previous powder diffraction study of Cs10Ta29.27O78 reported by Michel

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) x y z Uiso*/Ueq Occ.

inorganic compounds i12 Zeuner et al. doi:10.1107/S1600536809002967 Acta Cryst.

The title compound crystallizes isotypically with Rb5VONb14O38 (Haddad

View along [010] on the layers of the title compound connected via TaO6 octahedra. Displacement ellipsoids are drawn at the 50% probability level. caesium tantalate(V) Crystal data

Crossref

Cs10Ta29.27O78
Martin Zeuner, Alexander Hofer and Wolfgang Schnick*
Department Chemie und Biochemie, Ludwig-Maximilians-Universita¨t Mu¨nchen,
Lehrstuhl fu¨r Anorganische Festko¨rperchemie, Butenandtstrasse 5–13, D-81377
Mu¨nchen, Germany
Correspondence e-mail: wolfgang.schnick@uni-muenchen.de
Received 13 January 2009; accepted 23 January 2009
Key indicators: single-crystal X-ray study; T = 294 K; mean (Ta–O) = 0.010 A˚;
disorder in main residue; R factor = 0.033; wR factor = 0.083; data-to-parameter
ratio = 12.8.
Single crystals of caesium tantalate(V), Cs10Ta29.27O78, were
obtained as a serendipitous product in a welded tantalum
ampoule by a blank reaction of CsBr and bismuth subnitrate
[Bi5O(OH)9(NO3)4] with the container material. The crystal
structure of the title compound is made up of a three-
dimensional framework constituted by two types of layers, viz.
(Ta6O15)n and (Ta3O9)n, parallel to (001), which are linked
together by TaO6 octahedra (3m. symmetry) along [001]. This
framework has cavities where three independent Cs+ ions (3m.
and 6m2 symmetry, respectively) are located. The compound
reveals a Ta deficiency at one trigonal prismatic coordinated
site (6m2 symmetry). The composition of the title compound
was verified by energy-dispersive X-ray analysis of single
crystals.
Related literature
For a previous powder diffraction study of Cs10Ta29.27O78, see:
Michel et al. (1978). For an isotypic compound, see: Haddad &
Jouini (1997). For general background and related structures,
see: du Boulay et al. (2003); Magne´li (1953); Marini et al.
(1979); Serafin & Hoppe (1982).
Experimental
Crystal data
Cs10Ta29.27O78
Mr = 7873.51
Hexagonal, P63=mmc
a = 7.5170 (11) A˚
c = 36.340 (7) A˚
V = 1778.3 (5) A˚3
Z = 1
Mo K radiation
 = 49.96 mm1
T = 294 (2) K
0.03  0.02  0.01 mm
Data collection
Stoe IPDS-I diffractometer
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1999)
Tmin = 0.218, Tmax = 0.607
14043 measured reflections
855 independent reflections
587 reflections with I > 2(I)
Rint = 0.119
Refinement
R[F 2 > 2(F 2)] = 0.033
wR(F 2) = 0.083
S = 0.89
855 reflections
67 parameters
max = 1.54 e A˚
3
min = 3.28 e A˚3
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-
AREA; data reduction: X-AREA; program(s) used to solve structure:
SHELXS97 (Sheldrick, 2008); program(s) used to refine structure:
SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND
(Brandenburg, 1999); software used to prepare material for publi-
cation: SHELXL97.
The authors are indebted to Thomas Miller for performing
the single-crystal X-ray diffractometry. Financial support by
the Fonds der Chemischen Industrie is gratefully acknowl-
edged.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: WM2217).
References
Boulay, D. du, Oono, A. & Ishizawa, N. (2003). Acta Cryst. E59, i86–i88.
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Haddad, A. & Jouini, T. (1997). J. Solid State Chem. 25, 251–261.
Magne´li, A. (1953). Acta Chem. Scand. 7, 315–324.
Marini, A., Michel, C. & Raveau, B. (1979). J. Rev. Chim. Miner. 16, 73–79.
Michel, C., Guyomarch, A. & Raveau, B. (1978). J. Solid State Chem. 25, 251–
261.
Serafin, M. & Hoppe, R. (1982). Z. Anorg. Allg. Chem. 493, 77–92.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Stoe & Cie (1999). X-SHAPE. Stoe & Cie, Darmstadt, Germany.
Stoe & Cie (2002). X-AREA. Stoe & Cie, Darmstadt, Germany.
inorganic compounds
i12 Zeuner et al. doi:10.1107/S1600536809002967 Acta Cryst. (2009). E65, i12
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
supporting information
sup-1Acta Cryst. (2009). E65, i12    
supporting information
Acta Cryst. (2009). E65, i12    [doi:10.1107/S1600536809002967]
Cs10Ta29.27O78
Martin Zeuner, Alexander Hofer and Wolfgang Schnick
S1. Comment 
The title compound has a three-dimensional framework, constituted by two types of layers, (Ta6O15)n (Fig. 1, green) and 
(Ta3O9)n (Fig. 2, blue), parallel to (001). These layers are linked together along [001], according to the sequence (Ta6O15)n-
TaO6-(Ta3O9)n-(Ta3O9)n-TaO6, by sharing corners of TaO6 octahedra (red, Fig. 3). The tantalum atom with deficient 
occupation is located in a site with trigonal-prismatic coordinated sites (yellow), between two Ta3O9 units belonging to 
two neighboring (Ta3O9)n layers. This framework has cavities which communicate with interconnected channels, parallel 
to [100]. Cs+ ions (black) are located in these cavities. Geometric parameters of the title compound are in the usual 
ranges. Based on a previous powder diffraction study of Cs10Ta29.27O78 reported by Michel et al. (1978), an additional Ta 
site was found, but was not observed in the current re-investigation. The closely related structure of Tl10Nb29.2O78 was also 
reported (Marini et al., 1979) with an additional Nb site with too short interatomic distances between the Nb atoms.
The title compound crystallizes isotypically with Rb5VONb14O38 (Haddad & Jouini, 1997), in which the vanadium atom 
occupies the trigonal-prismatic Ta deficiency site of the title compound. The related compound Cs3Ta5O14 was first 
investigated by powder diffraction studies by Serafin & Hoppe (1982) and was later re-investigated on the basis of single-
crystal X-ray diffraction by du Boulay et al. (2003). An overview on the related hexagonal tungsten bronzes of potassium, 
rubidium and caesium was presented by Magnéli (1953).
S2. Experimental 
The title compound was obtained as a serendipitious product by the reaction of CsBr and bismuth subnitrate 
(Bi5O(OH)9(NO3)4, 98%, Sigma-Aldrich) with the tantalum container material. It was synthesized under argon at 
temperatures of 1523 K in a welded tantalum ampoule. The air stable title compound crystallizes in brown rods. The 
chemical composition of the single-crystal was confirmed by energy-dispersive X-ray (EDX) analysis which revealed no 
impurity elements.
S3. Refinement 
The site occupation factor (s.o.f.) of the Ta-deficient Ta4 site was refined freely. The maximum residual electron density 
lies 0.95 Å from O1 and the minimum residual electron density lies at the position of the Cs1 atom.
supporting information
sup-2Acta Cryst. (2009). E65, i12    
Figure 1
View along [001] on the (Ta6O15)n layer. 
Figure 2
View along [001] on the (Ta3O9)n layer. 
supporting information
sup-3Acta Cryst. (2009). E65, i12    
Figure 3
View along [010] on the layers of the title compound connected via TaO6 octahedra. Displacement ellipsoids are drawn at 
the 50% probability level. 
caesium tantalate(V) 
Crystal data 
Cs10Ta29.27O78
Mr = 7873.51
Hexagonal, P63/mmc
Hall symbol: -P 6c 2c
a = 7.5170 (11) Å
c = 36.340 (7) Å
V = 1778.3 (5) Å3
Z = 1
F(000) = 3310.4
Dx = 7.352 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1275 reflections
θ = 2.6–31.6°
µ = 49.96 mm−1
T = 294 K
Rod, brown
0.03 × 0.02 × 0.01 mm
supporting information
sup-4Acta Cryst. (2009). E65, i12    
Data collection 
Stoe IPDS-I 
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
Absorption correction: numerical 
(X-SHAPE; Stoe & Cie, 1999)
Tmin = 0.218, Tmax = 0.607
14043 measured reflections
855 independent reflections
587 reflections with I > 2σ(I)
Rint = 0.119
θmax = 27.5°, θmin = 3.1°
h = −9→9
k = −9→9
l = −46→46
Refinement 
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.033
wR(F2) = 0.083
S = 0.89
855 reflections
67 parameters
0 restraints
Primary atom site location: structure-invariant 
direct methods
Secondary atom site location: difference Fourier 
map
w = 1/[σ2(Fo2) + (0.0516P)2] 
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 1.54 e Å−3
Δρmin = −3.28 e Å−3
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) 
x y z Uiso*/Ueq Occ. (<1)
Ta1 0.0000 0.0000 0.11749 (3) 0.0166 (2)
Ta2 0.33551 (10) 0.16775 (5) 0.034126 (15) 0.01525 (19)
Ta3 0.17146 (6) 0.34292 (11) 0.196383 (17) 0.0204 (2)
Ta4 0.0000 0.0000 0.2500 0.0163 (8) 0.633 (10)
O1 0.0814 (19) 0.5407 (9) 0.1881 (4) 0.021 (2)
O2 0.5486 (9) 0.4514 (9) 0.0368 (3) 0.019 (2)
O3 0.1256 (9) 0.2511 (18) 0.1456 (3) 0.022 (2)
O4 0.2470 (17) 0.1235 (8) 0.0825 (3) 0.017 (2)
O5 0.1410 (8) −0.1410 (8) 0.0233 (3) 0.012 (2)
O6 0.2379 (18) 0.1190 (9) 0.2082 (3) 0.019 (2)
O7 0.1878 (15) 0.376 (3) 0.2500 0.023 (4)
Cs1 0.6667 0.3333 0.2500 0.0337 (6)
Cs2 0.3333 0.6667 0.08755 (7) 0.0459 (6)
Cs3 0.6667 0.3333 0.13681 (8) 0.0564 (7)
supporting information
sup-5Acta Cryst. (2009). E65, i12    
Atomic displacement parameters (Å2) 
U11 U22 U33 U12 U13 U23
Ta1 0.0158 (3) 0.0158 (3) 0.0180 (5) 0.00791 (16) 0.000 0.000
Ta2 0.0141 (3) 0.0144 (3) 0.0173 (3) 0.00703 (15) −0.0001 (2) −0.00005 (11)
Ta3 0.0181 (3) 0.0217 (4) 0.0226 (4) 0.01083 (19) −0.00299 (13) −0.0060 (3)
Ta4 0.0151 (10) 0.0151 (10) 0.0188 (13) 0.0075 (5) 0.000 0.000
O1 0.019 (5) 0.014 (4) 0.031 (6) 0.010 (3) −0.001 (5) 0.000 (2)
O2 0.020 (4) 0.020 (4) 0.022 (5) 0.013 (5) 0.002 (2) −0.002 (2)
O3 0.025 (5) 0.019 (6) 0.020 (5) 0.010 (3) 0.000 (2) 0.000 (4)
O4 0.016 (5) 0.016 (4) 0.019 (5) 0.008 (3) 0.007 (4) 0.004 (2)
O5 0.015 (4) 0.015 (4) 0.002 (4) 0.005 (4) −0.0019 (19) 0.0019 (19)
O6 0.016 (5) 0.013 (4) 0.028 (6) 0.008 (3) 0.000 (4) 0.000 (2)
O7 0.021 (6) 0.038 (11) 0.015 (7) 0.019 (5) 0.000 0.000
Cs1 0.0317 (9) 0.0317 (9) 0.0377 (15) 0.0159 (5) 0.000 0.000
Cs2 0.0443 (8) 0.0443 (8) 0.0493 (15) 0.0221 (4) 0.000 0.000
Cs3 0.0626 (11) 0.0626 (11) 0.0441 (14) 0.0313 (6) 0.000 0.000
Geometric parameters (Å, º) 
Ta1—O3 1.928 (12) Ta3—O7 1.960 (2)
Ta1—O3i 1.928 (12) Ta3—O6ii 2.028 (12)
Ta1—O3ii 1.928 (12) Ta3—O6 2.027 (10)
Ta1—O4i 2.050 (11) Ta3—Ta4 2.9631 (8)
Ta1—O4ii 2.050 (11) Ta4—O6i 2.170 (12)
Ta1—O4 2.050 (11) Ta4—O6ii 2.170 (12)
Ta2—O4 1.850 (11) Ta4—O6vii 2.170 (12)
Ta2—O2 1.925 (7) Ta4—O6 2.170 (12)
Ta2—O2iii 1.925 (8) Ta4—O6viii 2.170 (12)
Ta2—O5ii 2.070 (4) Ta4—O6ix 2.170 (12)
Ta2—O5 2.070 (4) Ta4—O7ii 2.45 (2)
Ta2—O5iv 2.114 (10) Ta4—O7 2.45 (2)
Ta2—Ta2v 3.3049 (10) Ta4—O7ix 2.446 (19)
Ta2—Ta2iv 3.3049 (10) Ta4—Ta3ii 2.9631 (8)
Ta3—O3 1.940 (12) Ta4—Ta3i 2.9631 (8)
Ta3—O1 1.941 (12) Ta4—Ta3vii 2.9631 (8)
Ta3—O1vi 1.941 (12)
O3—Ta1—O3i 94.5 (5) O3—Ta3—Ta4 113.2 (4)
O3—Ta1—O3ii 94.5 (5) O1—Ta3—Ta4 127.0 (4)
O3i—Ta1—O3ii 94.5 (5) O1vi—Ta3—Ta4 127.0 (4)
O3—Ta1—O4i 173.7 (5) O7—Ta3—Ta4 55.1 (6)
O3i—Ta1—O4i 89.8 (3) O6ii—Ta3—Ta4 47.1 (3)
O3ii—Ta1—O4i 89.8 (3) O6—Ta3—Ta4 47.1 (3)
O3—Ta1—O4ii 89.8 (3) O6i—Ta4—O6ii 76.4 (5)
O3i—Ta1—O4ii 173.7 (5) O6i—Ta4—O6vii 138.2 (2)
O3ii—Ta1—O4ii 89.8 (3) O6ii—Ta4—O6vii 138.2 (2)
O4i—Ta1—O4ii 85.6 (5) O6i—Ta4—O6 76.4 (5)
supporting information
sup-6Acta Cryst. (2009). E65, i12    
O3—Ta1—O4 89.8 (3) O6ii—Ta4—O6 76.4 (5)
O3i—Ta1—O4 89.8 (3) O6vii—Ta4—O6 88.9 (6)
O3ii—Ta1—O4 173.7 (5) O6i—Ta4—O6viii 138.2 (2)
O4i—Ta1—O4 85.6 (5) O6ii—Ta4—O6viii 88.9 (6)
O4ii—Ta1—O4 85.6 (5) O6vii—Ta4—O6viii 76.4 (5)
O4—Ta2—O2 100.2 (4) O6—Ta4—O6viii 138.2 (2)
O4—Ta2—O2iii 100.2 (4) O6i—Ta4—O6ix 88.9 (6)
O2—Ta2—O2iii 87.5 (7) O6ii—Ta4—O6ix 138.2 (2)
O4—Ta2—O5ii 89.5 (4) O6vii—Ta4—O6ix 76.4 (5)
O2—Ta2—O5ii 85.4 (4) O6—Ta4—O6ix 138.2 (2)
O2iii—Ta2—O5ii 168.9 (4) O6viii—Ta4—O6ix 76.4 (5)
O4—Ta2—O5 89.5 (4) O6i—Ta4—O7ii 69.09 (12)
O2—Ta2—O5 168.9 (4) O6ii—Ta4—O7ii 69.09 (12)
O2iii—Ta2—O5 85.4 (4) O6vii—Ta4—O7ii 135.5 (3)
O5ii—Ta2—O5 100.3 (6) O6—Ta4—O7ii 135.5 (3)
O4—Ta2—O5iv 152.4 (5) O6viii—Ta4—O7ii 69.09 (12)
O2—Ta2—O5iv 99.7 (4) O6ix—Ta4—O7ii 69.09 (12)
O2iii—Ta2—O5iv 99.7 (4) O6i—Ta4—O7 135.5 (3)
O5ii—Ta2—O5iv 73.2 (4) O6ii—Ta4—O7 69.09 (12)
O5—Ta2—O5iv 73.2 (4) O6vii—Ta4—O7 69.09 (12)
O4—Ta2—Ta2v 127.6 (2) O6—Ta4—O7 69.09 (12)
O2—Ta2—Ta2v 132.2 (3) O6viii—Ta4—O7 69.09 (12)
O2iii—Ta2—Ta2v 83.1 (3) O6ix—Ta4—O7 135.5 (3)
O5ii—Ta2—Ta2v 95.4 (3) O7ii—Ta4—O7 120.000 (1)
O5—Ta2—Ta2v 38.3 (3) O6i—Ta4—O7ix 69.09 (12)
O5iv—Ta2—Ta2v 37.37 (10) O6ii—Ta4—O7ix 135.5 (3)
O4—Ta2—Ta2iv 127.6 (2) O6vii—Ta4—O7ix 69.09 (12)
O2—Ta2—Ta2iv 83.1 (3) O6—Ta4—O7ix 69.09 (12)
O2iii—Ta2—Ta2iv 132.2 (3) O6viii—Ta4—O7ix 135.5 (3)
O5ii—Ta2—Ta2iv 38.3 (3) O6ix—Ta4—O7ix 69.09 (12)
O5—Ta2—Ta2iv 95.4 (3) O7ii—Ta4—O7ix 120.000 (1)
O5iv—Ta2—Ta2iv 37.37 (10) O7—Ta4—O7ix 120.000 (2)
Ta2v—Ta2—Ta2iv 69.83 (3) Ta3ii—Ta4—Ta3vii 135.741 (10)
O3—Ta3—O1 93.3 (4) Ta3i—Ta4—Ta3vii 135.741 (10)
O3—Ta3—O1vi 93.3 (5) Ta3—O1—Ta3x 140.3 (7)
O1—Ta3—O1vi 94.1 (7) Ta2—O2—Ta2xi 151.8 (7)
O3—Ta3—O7 168.3 (7) Ta1—O3—Ta3 139.9 (7)
O1—Ta3—O7 94.7 (5) Ta2—O4—Ta1 146.5 (7)
O1vi—Ta3—O7 94.7 (5) Ta2i—O5—Ta2 132.0 (6)
O3—Ta3—O6ii 88.8 (4) Ta2i—O5—Ta2v 104.3 (3)
O1—Ta3—O6ii 91.5 (5) Ta2—O5—Ta2v 104.3 (3)
O1vi—Ta3—O6ii 173.9 (5) Ta3i—O6—Ta3 145.0 (6)
O7—Ta3—O6ii 82.4 (6) Ta3i—O6—Ta4 89.8 (3)
O3—Ta3—O6 88.8 (4) Ta3—O6—Ta4 89.8 (3)
O1—Ta3—O6 173.9 (5) Ta3—O7—Ta3vii 167.5 (11)
O1vi—Ta3—O6 91.5 (5) Ta3—O7—Ta4 83.8 (6)
supporting information
sup-7Acta Cryst. (2009). E65, i12    
O7—Ta3—O6 82.4 (5) Ta3vii—O7—Ta4 83.8 (6)
O6ii—Ta3—O6 82.9 (6)
Symmetry codes: (i) −x+y, −x, z; (ii) −y, x−y, z; (iii) −y+1, x−y, z; (iv) x−y, x, −z; (v) y, −x+y, −z; (vi) −y+1, x−y+1, z; (vii) x, y, −z+1/2; (viii) −y, x−y, 
−z+1/2; (ix) −x+y, −x, −z+1/2; (x) −x+y, −x+1, z; (xi) −x+y+1, −x+1, z.


Cs
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http://journals.iucr.org/e/issues/2009/02/00/wm2217/wm2217.pdf

Cs10Ta29.27O78

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