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Acta Cryst. (2007). E63, i148    [ doi:10.1107/S1600536807024075 ]

(NH4)2(SO4)0.71(SeO4)0.29Te(OH)6

M. Abdelhedi, M. Dammak, A. Cousson, M. Jérome and K. Abdelwaheb

Abstract top

The main feature of the title structure, ammonium sulfate selenate tellurate, is the presence of three different chalcogenate species in the same compound. The crystal structure contains planes of SO4/SeO4 tetrahedra alternating with planes of Te(OH)6 octahedra. Disordered NH4+ cations are intercalated between these planes. Both octahedra and SO4/SeO4 tetrahedra are linked by O-H...O hydrogen bonds.

Comment top

In pursuing our study of sulfate selenate tellurate salts, amongst which we have solved Cs2(SO4)0.57(SeO4)0.43.Te(OH)6 (Abdelhedi, Dammak, Cousson, Nierlich & Abdelwaheb, 2005) and Rb2(SO4)0.5(SeO4)0.5.Te(OH)6 (Abdelhedi, Dammak, Cousson & Kolsi, 2005), we have grown the title compound, (NH4)2(SO4)0.71(SeO4)0.29.Te(OH)6 (NSSeTe). The structure (Fig. 1) is built up of planes of Te(OH)6 octahedra (at x = 0 and 1/2) alternating with planes of SO4/SeO4 tetrahedra (at x = 1/4 and 3/4), with disordered NH4 cations intercalated between these planes. The S and Se atoms occupy the same site. In the SO4/SeO4 tetrahedra, the S/Se—O distances range from 1.5165 (12) Å to 1.5246 (12) Å, intermediate between those in (NH4)2SO4.Te(OH)6 (1.373 (11)–1.565 (8) Å) (Zilber et al., 1981) and (NH4)2SeO4.Te(OH)6 (1.622 (4)–1.639 (4) Å) (Litaiem et al., 2005). In the octahedral groups, the Te—O distances vary from 1.9021 (13) to 1.9133 (11) Å with O—Te—O angles that range between 87.15 (5) and 92.85 (5)°. Each NH4 cation is coordinated to three oxygen atoms belonging to S/SeO4 tetrahedra and six oxygen atoms from Te(OH)6 octahedra. The structure is stabilized by O—H···O hydrogen bonds. The O···H distances in this compound vary from 1.7558 (12)Å to 1.897 (11)Å with O—H···O angles ranging from 155.47 (8)° to 172.90 (11)°. Figure 2 shows the packing arrangement of the NSSeTe material.

Related literature top

For related literature, see: Abdelhedi, Dammak, Cousson, Nierlich & Abdelwaheb et al. (2005); Abdelhedi, Dammak, Cousson & Kolsi (2005); Litaiem et al. (2005). _publ_section_exptl_refinement and _refine_ls_hydrogen_treatment entries say that H atoms were refined but no s.u. values are given for these parameters in the CIF; please clarify.

For related literature, see: Zilber et al. (1981).

Experimental top

Transparent, colorless single crystals of the title composition were grown from aqueous solution of a mixture of telluric acid, H6TeO6 (Aldrich, 99%), ammonium carbonate (NH4)2CO3, (Aldrich 99.9%), selenic acid, H2SeO4 (Aldrich 94%) and ammonium sulfate (NH4)2SO4, (Aldrich 99.999%) at room temperature. (The stoichiometric ratio 1:0.5:0.5:0.5).

Refinement top

Hydrogen atoms on Te(OH)6 groups were located in an electron density difference map and were refined isotropically. As a result of disorder, ammonium hydrogen atoms could not be found and therefore could not be included in the model.

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: CRYSTALS.

Figures top
[Figure 1] Fig. 1. A part of the structure of (NH4)2(SO4)0.71(SeO4)0.29Te(OH)6, showing the asymmetric unit (expanded by symmetry to give complete tellurate octahedra). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes:(a) -x + 1,-y, -z; b) -x, -y + 1, -z]
[Figure 2] Fig. 2. Crystal structure of (NH4)2(SO4)0.71(SeO4)0.29Te(OH)6 showing the hydrogen bonds.
Diammonium sulfate-selenate tellurate top
Crystal data top
2(NH4)+·O4S0.71Se0.292−·H6O6TeF(000) = 724.66
Mr = 385.23Dx = 2.552 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7138 reflections
a = 13.7340 (2) Åθ = 2.7–30.1°
b = 6.6583 (1) ŵ = 4.20 mm−1
c = 11.4582 (2) ÅT = 298 K
β = 106.827 (1)°Parallelepiped, colourless
V = 1002.93 (3) Å30.30 × 0.26 × 0.20 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		2213 reflections with I > 3σ(I)
graphiteRint = 0.030
φ rotation scans with 2°stepsθmax = 30.1°, θmin = 3.1°
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 1998)		h = −19→19
Tmin = 0.32, Tmax = 0.43k = −8→9
14354 measured reflectionsl = −16→16
2940 independent reflections
Refinement top
Refinement on FHydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.016 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 0.466 0.314 0.278
Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science. Springer-Verlag: New York. Watkin, D. (1994). Acta Cryst. A50, 411–437.
wR(F2) = 0.021(Δ/σ)max = 0.001
S = 1.01Δρmax = 0.64 e Å−3
2213 reflectionsΔρmin = −0.42 e Å−3
114 parametersExtinction correction: Larson 1970 Crystallographic Computing eq 22
1 restraintExtinction coefficient: 22.5 (17)
Primary atom site location: structure-invariant direct methods
Crystal data top
2(NH4)+·O4S0.71Se0.292−·H6O6TeV = 1002.93 (3) Å3
Mr = 385.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.7340 (2) ŵ = 4.20 mm−1
b = 6.6583 (1) ÅT = 298 K
c = 11.4582 (2) Å0.30 × 0.26 × 0.20 mm
β = 106.827 (1)°
Data collection top
Nonius KappaCCD
diffractometer		2940 independent reflections
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 1998)		2213 reflections with I > 3σ(I)
Tmin = 0.32, Tmax = 0.43Rint = 0.030
14354 measured reflectionsθmax = 30.1°
Refinement top
R[F2 > 2σ(F2)] = 0.016All H-atom parameters refined
wR(F2) = 0.021Δρmax = 0.64 e Å−3
S = 1.01Δρmin = −0.42 e Å−3
2213 reflectionsAbsolute structure: ?
114 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Te10.50000.00000.00000.0154
Te20.00000.50000.00000.0147
Se10.248690 (13)−0.010650 (13)0.233850 (13)0.01520.2869 (11)
S10.248690 (13)−0.010650 (13)0.233850 (13)0.01520.7131 (11)
N10.14479 (12)0.4841 (2)0.34630 (14)0.0278
N20.35360 (14)0.4953 (2)0.09225 (17)0.0352
O10.46433 (12)−0.0932 (2)0.13912 (13)0.0452
O20.63403 (8)−0.10532 (19)0.06867 (11)0.0283
O30.53678 (11)0.25802 (19)0.07172 (13)0.0401
O40.01747 (9)0.73221 (17)0.10219 (11)0.0261
O5−0.05209 (9)0.35904 (17)0.11395 (11)0.0268
O60.13448 (8)0.41154 (18)0.08537 (11)0.0246
O70.20637 (10)0.0546 (2)0.33679 (12)0.0331
O80.33787 (9)0.12668 (18)0.23575 (11)0.0285
O90.28331 (10)−0.22762 (18)0.25249 (11)0.0318
O100.16707 (10)0.00918 (17)0.11171 (11)0.0311
H10.4196−0.00210.16290.0380*
H20.6289−0.21260.12140.0450*
H30.60210.26400.12800.0470*
H40.07370.79400.09490.0470*
H5−0.09690.44460.14100.0440*
H60.13150.27180.10090.0550*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Te10.013986 (18)0.015896 (18)0.016686 (18)0.001266 (18)0.004796 (18)0.000916 (18)
Te20.015036 (18)0.015496 (18)0.014246 (18)−0.000284 (18)0.005266 (18)0.000376 (18)
Se10.014780 (13)0.015480 (13)0.015440 (13)−0.001180 (13)0.004510 (13)−0.000510 (13)
S10.014780 (13)0.015480 (13)0.015440 (13)−0.001180 (13)0.004510 (13)−0.000510 (13)
N10.0320 (7)0.0270 (7)0.0255 (6)0.0011 (5)0.0100 (6)−0.0006 (5)
N20.0403 (9)0.0311 (8)0.0371 (8)−0.0007 (6)0.0158 (7)−0.0002 (6)
O10.0571 (9)0.0488 (8)0.0440 (8)0.0286 (7)0.0374 (7)0.0248 (7)
O20.0180 (5)0.0303 (6)0.0351 (6)0.0045 (5)0.0053 (4)0.0070 (5)
O30.0372 (7)0.0227 (6)0.0469 (8)0.0033 (5)−0.0092 (6)−0.0090 (5)
O40.0263 (5)0.0244 (5)0.0293 (5)−0.0038 (4)0.0109 (4)−0.0098 (4)
O50.0324 (6)0.0246 (5)0.0295 (6)0.0026 (5)0.0187 (5)0.0077 (4)
O60.0184 (5)0.0256 (5)0.0272 (5)0.0021 (4)0.0025 (4)0.0013 (4)
O70.0347 (6)0.0374 (6)0.0337 (6)−0.0065 (5)0.0199 (5)−0.0074 (5)
O80.0280 (6)0.0287 (6)0.0320 (6)−0.0055 (5)0.0135 (5)−0.0047 (4)
O90.0306 (6)0.0244 (6)0.0360 (6)0.0017 (5)0.0028 (5)0.0016 (5)
O100.0319 (6)0.0267 (6)0.0288 (6)−0.0039 (5)−0.0005 (4)0.0018 (4)
Geometric parameters (Å, °) top
Te1—O2i1.9133 (11)Se1—O81.5236 (12)
Te1—O3i1.9083 (12)Se1—O91.5165 (12)
Te1—O1i1.9021 (13)Se1—O101.5246 (12)
Te1—O11.9021 (13)S1—O71.5213 (12)
Te1—O21.9133 (11)S1—O81.5236 (12)
Te1—O31.9083 (12)S1—O91.5165 (12)
Te2—O6ii1.9154 (10)S1—O101.5246 (12)
Te2—O4ii1.9122 (11)O1—H10.957
Te2—O5ii1.9075 (11)O2—H20.951
Te2—O41.9122 (11)O3—H30.942
Te2—O51.9075 (11)O4—H40.900
Te2—O61.9154 (10)O5—H50.954
Se1—O71.5213 (12)O6—H60.950
O2i—Te1—O3i92.85 (5)O4—Te2—O589.09 (5)
O2i—Te1—O1i89.22 (6)O6ii—Te2—O6179.994
O3i—Te1—O1i91.89 (7)O4ii—Te2—O689.75 (5)
O2i—Te1—O190.78 (6)O5ii—Te2—O690.21 (5)
O3i—Te1—O188.11 (7)O4—Te2—O690.25 (5)
O1i—Te1—O1179.994O5—Te2—O689.79 (5)
O2i—Te1—O2179.994O7—Se1—O8107.68 (7)
O3i—Te1—O287.15 (5)O7—Se1—O9109.71 (8)
O1i—Te1—O290.78 (6)O8—Se1—O9110.59 (7)
O1—Te1—O289.22 (6)O7—Se1—O10110.04 (8)
O2i—Te1—O387.15 (5)O8—Se1—O10109.60 (7)
O3i—Te1—O3179.994O9—Se1—O10109.21 (6)
O1i—Te1—O388.11 (7)O7—S1—O8107.68 (7)
O1—Te1—O391.89 (7)O7—S1—O9109.71 (8)
O2—Te1—O392.85 (5)O8—S1—O9110.59 (7)
O6ii—Te2—O4ii90.25 (5)O7—S1—O10110.04 (8)
O6ii—Te2—O5ii89.79 (5)O8—S1—O10109.60 (7)
O4ii—Te2—O5ii89.09 (5)O9—S1—O10109.21 (6)
O6ii—Te2—O489.75 (5)Te1—O1—H1111.974
O4ii—Te2—O4179.994Te1—O2—H2107.281
O5ii—Te2—O490.91 (5)Te1—O3—H3114.442
O6ii—Te2—O590.21 (5)Te2—O4—H4105.768
O4ii—Te2—O590.91 (5)Te2—O5—H5109.488
O5ii—Te2—O5179.994Te2—O6—H6108.017
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD—H···A
O1—H1···O80.9572 (13)1.7984 (12)166.50 (9)
O2—H2···O8iii0.9512 (12)1.8974 (11)158.11 (8)
O3—H3···O9iv0.9420 (13)1.7628 (12)172.90 (11)
O4—H4···O10v0.9000 (11)1.8951 (12)155.47 (8)
O5—H5···O7vi0.9538 (12)1.7558 (12)162.99 (9)
O6—H6···O100.9504 (12)1.8101 (12)158.93 (8)
Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x, y+1, z; (vi) −x, y+1/2, −z+1/2.
Acknowledgements top

This project was supported by the French Ministry of Research and New Technologies and the French/Tunisian Twin Committee for University Collaboration

references
References top

Abdelhedi, M., Dammak, M., Cousson, A. & Kolsi, A. W. (2005). J. Alloys Compd. 398, 55–61. Kolsi, A. W. or Abdelwaheb, K.?

Abdelhedi, M., Dammak, M., Cousson, A., Nierlich, M. & Abdelwaheb, K. (2005). Acta Cryst. E61, i256–i258.

Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487–?.

Brandenburg, K. & Berndt, M. (1999). DIAMOND. Version 2.1.b. Crystal Impact GbR, Bonn, Germany.

Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, p. 29. Copenhagen: Munksgaard.

Litaiem, H., Dammak, M., Mhiri, T. & Cousson, A. (2005). J. Alloys Compd. 396, 34–39.

Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science. Springer-Verlag: New York.

Sheldrick, G. M. (1986). SHELXS86. University of Göttingen, Germany.

Spek, A. L. (1998). PLATON. University of Utrecht, The Netherlands.

Watkin, D. (1994). Acta Cryst. A50, 411–437.

Zilber, R., Durif, A. & Averbuch-Pouchot, M. T. (1981). Acta Cryst. B37, 650–652.