Acta Cryst. (2007). E63, i153-i154 [ doi:10.1107/S1600536807027705 ]
The title compound, dipotassium sulfate selenate/telluric acid adduct, K2(SO4)0.63(SeO4)0.47·Te(OH)6, is a solid solution in the series K2SO4·Te(OH)6/K2SeO4·Te(OH)6. It crystallizes in the same structure as the end member K2SO4·Te(OH)6 in the space group P
, whereas the other end-member K2SeO4·Te(OH)6 crystallizes in the space group C2/c. The structure of the solid solution consists of planes of Te(OH)6 octahedra alternating with planes of statistically occupied XO4 tetrahedra (X = S and Se), and with K+ cations situated between the planes. The structure is stabilized by interplanar O-H
O hydrogen bonds involving all the H atoms that belong to the OH groups of the Te(OH)6 octahedra. Both Te atoms lie on inversion centres.
Transparent, colorless single crystals of compound (I) were grown at room temperature by slow evaporation of an aqueous solution consisting of a mixture of Te(OH)6 (Aldrich, 99%), K2SeO4 (Aldrich, 99.99%) and K2SO4 (Aldrich, 99%) in the stoichiometric ratio 1:0.5:0.5.
Hydrogen atoms on Te(OH)6 groups were located in a difference map and were refined with restrained distances between 0.81 (1) and 0.86 (1) Å and a common Uiso parameter. For the refinement of the occupation factors for S and Se, their sum was constrained to be equal to 1. The highest peak and the deepest hole in the final Fourier map are located 0.04 and 0.57 Å, respectively, from the X site (X = S, Se).
Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); 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.
![[Figure 1]](./wm2119fig1thm.gif)
| Fig. 1. Projection of the K2(SO4)0.63(SeO4)0.37·Te(OH)6 crystal structure on the ab plane. |
![[Figure 2]](./wm2119fig2thm.gif)
| Fig. 2. The asymmetric unit of K2(SO4)0.63(SeO4)0.37·Te(OH)6 (expanded by symmetry to give complete Te(OH)6 octahedra) with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes:(a) −x, −y, −z; (b) −x + 1, −y, −z + 1]. |
![[Figure 3]](./wm2119fig3thm.gif)
| Fig. 3. The hydrogen bonding (dotted lines) in the crystal structure of K2(SO4)0.63(SeO4)0.37·Te(OH)6. |
| K2(SO4)0.63(SeO4)0.37Te(OH)6 | Z = 2 |
| Mr = 421.16 | F000 = 397.250 |
| Triclinic, P1 | Dx = 2.961 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 6.2463 (2) Å | Cell parameters from 7138 reflections |
| b = 6.6470 (2) Å | θ = 2.7–30.1º |
| c = 13.1326 (4) Å | µ = 5.63 mm−1 |
| α = 102.138 (2)º | T = 298 K |
| β = 90.073 (2)º | Prism, colourless |
| γ = 116.943 (1)º | 0.15 × 0.14 × 0.10 mm |
| V = 472.28 (3) Å3 |
| Nonius KappaCCD diffractometer | 1719 reflections with I > 3σ(I) |
| Monochromator: graphite | Rint = 0.038 |
| T = 298 K | θmax = 30.2º |
| φ rotation scans with 2° width | θmin = 1.6º |
| Absorption correction: multi-scan (MULABS in PLATON; Spek, 2003) | h = −8→8 |
| Tmin = 0.447, Tmax = 0.569 | k = −9→9 |
| 69116 measured reflections | l = −18→18 |
| 2787 independent reflections |
| Refinement on F | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.045 | All H-atom parameters refined |
| wR(F2) = 0.051 | Method, part 1, Chebychev polynomial, [Watkin (1994). Acta Cryst.
A50, 411–437; Prince,
(1982). Mathematical Techniques in Crystallography and Materials
Science. Springer-Verlag: New York.]
[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: 4.11 -3.38 2.64 |
| S = 1.09 | (Δ/σ)max = 0.002 |
| 1719 reflections | Δρmax = 2.40 e Å−3 |
| 114 parameters | Δρmin = −2.99 e Å−3 |
| 7 restraints | Extinction correction: None |
| K2(SO4)0.63(SeO4)0.37Te(OH)6 | γ = 116.943 (1)º |
| Mr = 421.16 | V = 472.28 (3) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.2463 (2) Å | Mo Kα |
| b = 6.6470 (2) Å | µ = 5.63 mm−1 |
| c = 13.1326 (4) Å | T = 298 K |
| α = 102.138 (2)º | 0.15 × 0.14 × 0.10 mm |
| β = 90.073 (2)º |
| Nonius KappaCCD diffractometer | 2787 independent reflections |
| Absorption correction: multi-scan (MULABS in PLATON; Spek, 2003) | 1719 reflections with I > 3σ(I) |
| Tmin = 0.447, Tmax = 0.569 | Rint = 0.038 |
| 69116 measured reflections |
| R[F2 > 2σ(F2)] = 0.045 | 7 restraints |
| wR(F2) = 0.051 | All H-atom parameters refined |
| S = 1.09 | Δρmax = 2.40 e Å−3 |
| 1719 reflections | Δρmin = −2.99 e Å−3 |
| 114 parameters |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Te1 | 0.0000 | 0.0000 | 0.0000 | 0.0150 | |
| Te2 | 0.5000 | 0.0000 | 0.5000 | 0.0144 | |
| Se1 | −0.24991 (17) | 0.46625 (17) | 0.24814 (17) | 0.0439 | 0.368 (7) |
| S1 | −0.24991 (17) | 0.46625 (17) | 0.24814 (17) | 0.0439 | 0.632 (7) |
| K1 | 0.1921 (4) | 0.2576 (3) | 0.35079 (18) | 0.0274 | |
| K2 | 0.4207 (4) | −0.2342 (3) | 0.14873 (17) | 0.0254 | |
| O1 | −0.0604 (11) | −0.0373 (10) | 0.1399 (5) | 0.0232 | |
| O2 | −0.1770 (12) | 0.1704 (11) | 0.0061 (5) | 0.0251 | |
| O3 | 0.2905 (11) | 0.2817 (10) | 0.0548 (6) | 0.0269 | |
| O4 | 0.7680 (10) | −0.0037 (10) | 0.4321 (5) | 0.0250 | |
| O5 | 0.6055 (11) | 0.3137 (9) | 0.4891 (5) | 0.0215 | |
| O6 | 0.3083 (10) | −0.1107 (10) | 0.3668 (5) | 0.0233 | |
| O7 | −0.1044 (11) | 0.4714 (11) | 0.3412 (5) | 0.0260 | |
| O8 | −0.3641 (13) | 0.6150 (12) | 0.2807 (6) | 0.0281 | |
| O9 | −0.0842 (12) | 0.5509 (12) | 0.1687 (6) | 0.0312 | |
| O10 | −0.4411 (12) | 0.2270 (10) | 0.2057 (6) | 0.0301 | |
| H1 | −0.0693 | −0.1671 | 0.1452 | 0.0436* | |
| H2 | −0.1419 | 0.2746 | 0.0589 | 0.0436* | |
| H3 | 0.3657 | 0.2491 | 0.0937 | 0.0436* | |
| H4 | 0.7229 | −0.1343 | 0.3896 | 0.0436* | |
| H5 | 0.6985 | 0.3395 | 0.4404 | 0.0436* | |
| H6 | 0.1875 | −0.2315 | 0.3702 | 0.0436* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Te1 | 0.01489 (9) | 0.01533 (9) | 0.01406 (9) | 0.00653 (9) | 0.00131 (9) | 0.00335 (9) |
| Te2 | 0.01472 (9) | 0.01349 (9) | 0.01512 (9) | 0.00649 (9) | 0.00155 (9) | 0.00350 (9) |
| Se1 | 0.03752 (17) | 0.04897 (17) | 0.03836 (17) | 0.01470 (17) | 0.00249 (17) | 0.00931 (17) |
| S1 | 0.03752 (17) | 0.04897 (17) | 0.03836 (17) | 0.01470 (17) | 0.00249 (17) | 0.00931 (17) |
| K1 | 0.0242 (8) | 0.0260 (8) | 0.0370 (11) | 0.0156 (7) | 0.0043 (7) | 0.0079 (7) |
| K2 | 0.0244 (8) | 0.0227 (8) | 0.0346 (10) | 0.0146 (7) | 0.0013 (7) | 0.0093 (7) |
| O1 | 0.033 (3) | 0.025 (3) | 0.016 (3) | 0.015 (2) | 0.007 (2) | 0.009 (2) |
| O2 | 0.031 (3) | 0.028 (3) | 0.024 (3) | 0.022 (3) | 0.000 (2) | 0.003 (2) |
| O3 | 0.025 (3) | 0.016 (2) | 0.035 (4) | 0.004 (2) | −0.007 (2) | 0.008 (2) |
| O4 | 0.019 (3) | 0.020 (3) | 0.032 (3) | 0.008 (2) | 0.008 (2) | 0.001 (2) |
| O5 | 0.026 (3) | 0.013 (2) | 0.026 (3) | 0.009 (2) | 0.006 (2) | 0.006 (2) |
| O6 | 0.024 (3) | 0.019 (3) | 0.020 (3) | 0.004 (2) | −0.004 (2) | 0.006 (2) |
| O7 | 0.023 (3) | 0.031 (3) | 0.028 (3) | 0.011 (2) | 0.000 (2) | 0.017 (3) |
| O8 | 0.036 (4) | 0.032 (3) | 0.029 (4) | 0.029 (3) | 0.006 (3) | 0.001 (3) |
| O9 | 0.032 (3) | 0.030 (3) | 0.033 (4) | 0.013 (3) | 0.006 (3) | 0.012 (3) |
| O10 | 0.031 (3) | 0.016 (3) | 0.038 (4) | 0.007 (2) | −0.005 (3) | 0.005 (2) |
| Te1—O1i | 1.920 (6) | O4—H4 | 0.848 |
| Te1—O3i | 1.915 (6) | O5—H5 | 0.856 |
| Te1—O2i | 1.900 (6) | O6—H6 | 0.826 |
| Te1—O1 | 1.920 (6) | K1—O4iii | 2.792 (6) |
| Te1—O2 | 1.900 (6) | K1—O7 | 2.815 (6) |
| Te1—O3 | 1.915 (6) | K1—O5iv | 2.889 (6) |
| Te2—O6ii | 1.921 (6) | K1—O6 | 2.897 (6) |
| Te2—O5ii | 1.919 (5) | K1—O1 | 2.984 (7) |
| Te2—O4ii | 1.905 (6) | K1—O5 | 2.990 (6) |
| Te2—O4 | 1.905 (6) | K1—O8v | 3.022 (8) |
| Te2—O5 | 1.919 (5) | K1—O10v | 3.032 (8) |
| Te2—O6 | 1.921 (6) | K2—O10v | 2.709 (6) |
| X1—O7 | 1.508 (6) | K2—O2i | 2.751 (6) |
| X1—O8 | 1.460 (7) | K2—O8vi | 2.786 (8) |
| X1—O9 | 1.482 (7) | K2—O9vii | 2.852 (7) |
| X1—O10 | 1.473 (6) | K2—O1v | 2.908 (7) |
| O1—H1 | 0.857 | K2—O3vii | 2.915 (6) |
| O2—H2 | 0.817 | K2—O6 | 2.984 (7) |
| O3—H3 | 0.817 | K2—O3viii | 3.267 (8) |
| O1i—Te1—O3i | 89.9 (3) | O6ii—Te2—O5 | 90.4 (3) |
| O1i—Te1—O2i | 91.2 (3) | O5ii—Te2—O5 | 179.994 |
| O3i—Te1—O2i | 90.4 (3) | O4ii—Te2—O5 | 90.0 (3) |
| O1i—Te1—O1 | 179.994 | O4—Te2—O5 | 90.0 (3) |
| O3i—Te1—O1 | 90.1 (3) | O6ii—Te2—O6 | 179.994 |
| O2i—Te1—O1 | 88.8 (3) | O5ii—Te2—O6 | 90.4 (3) |
| O1i—Te1—O2 | 88.8 (3) | O4ii—Te2—O6 | 89.6 (3) |
| O3i—Te1—O2 | 89.6 (3) | O4—Te2—O6 | 90.4 (3) |
| O2i—Te1—O2 | 179.994 | O5—Te2—O6 | 89.6 (3) |
| O1—Te1—O2 | 91.2 (3) | O7—X1—O8 | 109.8 (4) |
| O1i—Te1—O3 | 90.1 (3) | O7—X1—O9 | 108.3 (4) |
| O3i—Te1—O3 | 179.994 | O8—X1—O9 | 110.1 (4) |
| O2i—Te1—O3 | 89.6 (3) | O7—X1—O10 | 109.3 (4) |
| O1—Te1—O3 | 89.9 (3) | O8—X1—O10 | 108.4 (4) |
| O2—Te1—O3 | 90.4 (3) | O9—X1—O10 | 111.0 (4) |
| O6ii—Te2—O5ii | 89.6 (3) | Te1—O1—H1 | 109.426 |
| O6ii—Te2—O4ii | 90.4 (3) | Te1—O2—H2 | 114.986 |
| O5ii—Te2—O4ii | 90.0 (3) | Te1—O3—H3 | 105.734 |
| O6ii—Te2—O4 | 89.6 (3) | Te2—O4—H4 | 109.438 |
| O5ii—Te2—O4 | 90.0 (3) | Te2—O5—H5 | 108.396 |
| O4ii—Te2—O4 | 179.994 | Te2—O6—H6 | 106.016 |
| Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z; (vi) x+1, y−1, z; (vii) x, y−1, z; (viii) −x+1, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O9vii | 0.857 (6) | 1.924 (7) | 2.780 (9) | 175.6 (5) |
| O2—H2···O9 | 0.817 (6) | 1.967 (7) | 2.773 (10) | 168.7 (5) |
| O3—H3···O10v | 0.817 (6) | 1.972 (7) | 2.778 (9) | 169.1 (5) |
| O4—H4···O8vi | 0.848 (6) | 1.815 (7) | 2.654 (9) | 169.7 (5) |
| O5—H5···O7v | 0.856 (6) | 1.868 (6) | 2.701 (9) | 164.3 (4) |
| O6—H6···O7vii | 0.826 (6) | 1.946 (6) | 2.755 (8) | 166.0 (5) |
| Symmetry codes: (vii) x, y−1, z; (v) x+1, y, z; (vi) x+1, y−1, z. |
| Te1—O1i | 1.920 (6) | K1—O4iii | 2.792 (6) |
| Te1—O3i | 1.915 (6) | K1—O7 | 2.815 (6) |
| Te1—O2i | 1.900 (6) | K1—O5iv | 2.889 (6) |
| Te1—O1 | 1.920 (6) | K1—O6 | 2.897 (6) |
| Te1—O2 | 1.900 (6) | K1—O1 | 2.984 (7) |
| Te1—O3 | 1.915 (6) | K1—O5 | 2.990 (6) |
| Te2—O6ii | 1.921 (6) | K1—O8v | 3.022 (8) |
| Te2—O5ii | 1.919 (5) | K1—O10v | 3.032 (8) |
| Te2—O4ii | 1.905 (6) | K2—O10v | 2.709 (6) |
| Te2—O4 | 1.905 (6) | K2—O2i | 2.751 (6) |
| Te2—O5 | 1.919 (5) | K2—O8vi | 2.786 (8) |
| Te2—O6 | 1.921 (6) | K2—O9vii | 2.852 (7) |
| X1—O7 | 1.508 (6) | K2—O1v | 2.908 (7) |
| X1—O8 | 1.460 (7) | K2—O3vii | 2.915 (6) |
| X1—O9 | 1.482 (7) | K2—O6 | 2.984 (7) |
| X1—O10 | 1.473 (6) | K2—O3viii | 3.267 (8) |
| Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z; (vi) x+1, y−1, z; (vii) x, y−1, z; (viii) −x+1, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O9vii | 0.857 (6) | 1.924 (7) | 2.780 (9) | 175.6 (5) |
| O2—H2···O9 | 0.817 (6) | 1.967 (7) | 2.773 (10) | 168.7 (5) |
| O3—H3···O10v | 0.817 (6) | 1.972 (7) | 2.778 (9) | 169.1 (5) |
| O4—H4···O8vi | 0.848 (6) | 1.815 (7) | 2.654 (9) | 169.7 (5) |
| O5—H5···O7v | 0.856 (6) | 1.868 (6) | 2.701 (9) | 164.3 (4) |
| O6—H6···O7vii | 0.826 (6) | 1.946 (6) | 2.755 (8) | 166.0 (5) |
| Symmetry codes: (vii) x, y−1, z; (v) x+1, y, z; (vi) x+1, y−1, z. |
This project was supported by the French Ministry of Research & New Technologies and the French/Tunisian Twin Comity for University collaboration.
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.
Dammak, M., Cousson, A. & Nierlich, M. (2005). Acta Cryst. E61, i55–i57.
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.
Sheldrick, G. M. (1997). SHELXS97. University of Göttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Zilber, R., Tordjman, I. & Guitel, J. C. (1980). Acta Cryst. B36, 2741–2743.
Fig. 1 shows a projection of the title structure (I) on the ab plane. The structure consists of planes of Te(OH)6 octahedra alternating with planes of statistically occupied XO4 tetrahedra (X = S, Se). The Te(OH)6 layers extend parallel to the ac plane at y = 0, whereas the parallel XO4 layers are at y ≈ 0.5. The K+ cations are situated between the layers.
The two independent Te atoms in (I) occupy inversion centres (Fig. 2), with very similar Te—O distances between 1.900 (6) and 1.921 (6) Å and O—Te—O angles between 88.8 (3) and 91.20 (3)°. In the isostructural end-member K2SO4·Te(OH)6 (KSTe) (Zilber et al., 1980), the Te—O distances are nearly the same and vary from 1.914 (5) to 1.938 (5) Å, whilst in K2SeO4·Te(OH)6 (KSeTe) they are between 1.913 (2) and 1.919 (2) Å (Dammak et al., 2005).
The X—O distances of the slightly distorted XO4 tetrahedra vary from 1.460 (7) to 1.508 (6) Å, with O—X—O angles between 108.3 (4) and 111.0 (4)°. In the KSTe structure, the S—O distances range from 1.453 (5) to 1.503 (5) Å and in the KSeTe homologue, the Se—O distances vary from 1.627 (7) to 1.659 (7) Å.
The two K+ cations are both in eightfold coordination with distances ranging between 2.709 (6) and 3.267 (8) Å. K1+ is coordinated by three O atoms belonging to two XO4 tetrahedra, by one O atom of a Te1O6 octahedron, and by four O atoms of three Te2O6 octahedra. The environment of K2+ consists of three O atoms belonging to three XO4 tetrahedra, of one O atom from a Te2O6 octahedron, and of four O atoms from three Te1O6 octahedra.
Interplanar O—H···O hydrogen bonding between the Te(OH)6 octahedra and the XO4 tetrahedra helps to consolidate the structural set-up. In consequence, all H atoms of the hydroxyl groups participate in the formation of hydrogen bonding. In the XO4 group, two oxygen atoms are acceptors of one H atom, whereas the other O atoms are acceptors of two H atoms. The O···O distances vary from 2.654 (9) to 2.780 (9) Å and the O—H···O angles range from 164.3 (4) and 175.6 (5)° (Table 1, Fig. 3).