Acta Cryst. (2008). E64, m1027 [ doi:10.1107/S160053680802120X ]
The anion of the title compound, also called sygethin dihydrate, 2K+·C18H20O6S22-·2H2O, has crystallographic inversion symmetry. The K+ cation is surrounded by eight O atoms in a distorted cubic coordination geometry, forming extended K-O-S networks. There are also O-H
O hydrogen bonds.
The title compound was supplied by Grindeks Company. To grow crystals suitable for single-crystal diffraction study, the powder form of sygethin dihydrate was dissolved in water at 333 K to obtain a saturated solution. After filtration, the saturated solution was diluted with approximately 50% more water and allowed to crystallize in a petri dish at ambient temperature.
The hydrogen atoms were all located in a difference Fourier map. Hydrogen atoms attached to carbon atoms were repositioned goemetrically. During refinement, hydrogen atoms were constrained to the riding mode. Uiso(H)=xUeq(C,O), where the average values of x are 1.66 for H atoms of the methyl group, 1.2 to 1.29 for H atoms attached to the remaining C atom, and 1.41 for the H atoms of the water molecule.
Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
![[Figure 1]](./cf2208fig1thm.gif)
| Fig. 1. The structure of the title compound, with displacement ellipsoids at the 50% probability level. [Symmetry code for unlabeled atoms: 1-x, -y, -z.] |
![[Figure 2]](./cf2208fig2thm.gif)
| Fig. 2. Packing diagram of the title compound. |
| 2K+·C18H20O6S22–·2H2O | Z = 1 |
| Mr = 255.36 | F000 = 266 |
| Triclinic, P1 | Dx = 1.497 Mg m−3 Dm = Mg m−3 Dm measured by ? |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 5.8741 (5) Å | Cell parameters from 2576 reflections |
| b = 6.5684 (5) Å | θ = 1.4–27.4º |
| c = 15.2335 (14) Å | µ = 0.64 mm−1 |
| α = 84.272 (4)º | T = 298 K |
| β = 83.768 (5)º | Prism, colourless |
| γ = 76.522 (6)º | 0.27 × 0.19 × 0.14 mm |
| V = 566.51 (8) Å3 |
| Nonius KappaCCD diffractometer | 1918 reflections with I > 2σ(I) |
| Radiation source: Enhance (Mo) X-ray Source | Rint = 0.027 |
| Monochromator: graphite | θmax = 27.4º |
| T = 298 K | θmin = 1.4º |
| φ and ω scans | h = −7→7 |
| Absorption correction: none | k = −8→8 |
| 4330 measured reflections | l = −18→19 |
| 2576 independent reflections |
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = [1-(Fo-Fc)2/36σ2(F)]2/[53.8T0(x) + 84.3T1(x) + 51.6T2(x) + 20.0T3(x) + 5.48T4(x)]
where Ti are Chebychev polynomials and x = Fc/Fmax |
| R[F2 > 2σ(F2)] = 0.051 | (Δ/σ)max = 0.0003 |
| wR(F2) = 0.122 | Δρmax = 1.49 e Å−3 |
| S = 0.89 | Δρmin = −0.42 e Å−3 |
| 1918 reflections | Extinction correction: none |
| 137 parameters |
| 2K+·C18H20O6S22–·2H2O | γ = 76.522 (6)º |
| Mr = 255.36 | V = 566.51 (8) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 5.8741 (5) Å | Mo Kα |
| b = 6.5684 (5) Å | µ = 0.64 mm−1 |
| c = 15.2335 (14) Å | T = 298 K |
| α = 84.272 (4)º | 0.27 × 0.19 × 0.14 mm |
| β = 83.768 (5)º |
| Nonius KappaCCD diffractometer | 2576 independent reflections |
| Absorption correction: none | 1918 reflections with I > 2σ(I) |
| 4330 measured reflections | Rint = 0.027 |
| R[F2 > 2σ(F2)] = 0.051 | 137 parameters |
| wR(F2) = 0.122 | H-atom parameters constrained |
| S = 0.89 | Δρmax = 1.49 e Å−3 |
| 1918 reflections | Δρmin = −0.42 e Å−3 |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.5804 (7) | −0.0364 (6) | 0.0370 (2) | 0.0454 | |
| C2 | 0.4756 (6) | 0.0667 (5) | 0.1221 (2) | 0.0398 | |
| C3 | 0.5685 (7) | 0.2183 (5) | 0.1527 (2) | 0.0455 | |
| C4 | 0.4714 (7) | 0.3172 (5) | 0.2292 (2) | 0.0431 | |
| C5 | 0.2797 (5) | 0.2595 (5) | 0.27676 (19) | 0.0324 | |
| S6 | 0.15644 (14) | 0.37197 (12) | 0.37713 (5) | 0.0329 | |
| O7 | 0.1593 (5) | 0.1938 (4) | 0.44237 (15) | 0.0503 | |
| O8 | −0.0830 (4) | 0.4813 (4) | 0.36269 (17) | 0.0476 | |
| O9 | 0.3068 (5) | 0.5041 (5) | 0.39615 (18) | 0.0554 | |
| C10 | 0.1865 (7) | 0.1054 (7) | 0.2483 (2) | 0.0490 | |
| C11 | 0.2858 (7) | 0.0092 (8) | 0.1721 (3) | 0.0564 | |
| C12 | 0.6723 (9) | −0.2695 (7) | 0.0533 (3) | 0.0589 | |
| C13 | 0.8749 (8) | −0.3309 (7) | 0.1140 (3) | 0.0603 | |
| K14 | 0.67561 (14) | 0.20792 (11) | 0.48854 (5) | 0.0427 | |
| O15 | 0.3244 (5) | 0.1011 (4) | 0.62693 (19) | 0.0594 | |
| H11 | 0.7195 | 0.0235 | 0.0172 | 0.0592* | |
| H31 | 0.7003 | 0.2542 | 0.1201 | 0.0587* | |
| H41 | 0.5361 | 0.4240 | 0.2493 | 0.0543* | |
| H101 | 0.0552 | 0.0653 | 0.2817 | 0.0628* | |
| H111 | 0.2199 | −0.0957 | 0.1524 | 0.0748* | |
| H121 | 0.7280 | −0.3309 | −0.0033 | 0.0684* | |
| H122 | 0.5410 | −0.3272 | 0.0825 | 0.0689* | |
| H131 | 0.9207 | −0.4839 | 0.1192 | 0.0894* | |
| H132 | 1.0067 | −0.2743 | 0.0867 | 0.0891* | |
| H133 | 0.8213 | −0.2757 | 0.1713 | 0.0894* | |
| H5 | 0.2249 | 0.2110 | 0.6406 | 0.0828* | |
| H13 | 0.4165 | 0.0717 | 0.6665 | 0.0829* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.053 (2) | 0.050 (2) | 0.0306 (16) | −0.0163 (14) | 0.0018 (14) | −0.0036 (16) |
| C2 | 0.0498 (19) | 0.0424 (18) | 0.0251 (14) | −0.0110 (13) | −0.0015 (12) | −0.0038 (15) |
| C3 | 0.066 (2) | 0.0375 (17) | 0.0340 (16) | −0.0099 (13) | 0.0122 (15) | −0.0186 (17) |
| C4 | 0.062 (2) | 0.0350 (16) | 0.0350 (16) | −0.0118 (13) | 0.0071 (15) | −0.0172 (16) |
| C5 | 0.0360 (15) | 0.0342 (15) | 0.0247 (13) | −0.0073 (11) | −0.0044 (11) | −0.0006 (13) |
| S6 | 0.0364 (4) | 0.0328 (4) | 0.0272 (4) | −0.0097 (3) | −0.0024 (3) | 0.0000 (3) |
| O7 | 0.0666 (17) | 0.0453 (14) | 0.0291 (12) | −0.0015 (10) | 0.0008 (11) | 0.0045 (13) |
| O8 | 0.0413 (14) | 0.0446 (14) | 0.0498 (14) | −0.0112 (11) | −0.0066 (11) | 0.0089 (11) |
| O9 | 0.0584 (17) | 0.0668 (18) | 0.0492 (15) | −0.0335 (13) | 0.0058 (12) | −0.0235 (14) |
| C10 | 0.0441 (19) | 0.068 (2) | 0.0424 (18) | −0.0273 (17) | 0.0078 (15) | −0.0226 (18) |
| C11 | 0.053 (2) | 0.080 (3) | 0.049 (2) | −0.039 (2) | 0.0069 (16) | −0.032 (2) |
| C12 | 0.073 (3) | 0.055 (2) | 0.049 (2) | −0.0125 (18) | 0.0002 (19) | −0.014 (2) |
| C13 | 0.062 (3) | 0.054 (2) | 0.066 (3) | −0.005 (2) | −0.016 (2) | −0.010 (2) |
| K14 | 0.0488 (5) | 0.0328 (4) | 0.0463 (4) | −0.0084 (3) | −0.0041 (3) | −0.0066 (3) |
| O15 | 0.0713 (19) | 0.0425 (14) | 0.0553 (16) | −0.0111 (12) | −0.0175 (14) | 0.0138 (13) |
| C1—C1i | 1.518 (7) | C11—H111 | 0.952 |
| C1—C2 | 1.525 (4) | C12—C13 | 1.542 (6) |
| C1—C12 | 1.505 (6) | C12—H121 | 0.980 |
| C1—H11 | 0.993 | C12—H122 | 0.982 |
| C2—C3 | 1.382 (5) | C13—H131 | 0.975 |
| C2—C11 | 1.386 (5) | C13—H132 | 0.972 |
| C3—C4 | 1.393 (4) | C13—H133 | 0.971 |
| C3—H31 | 0.938 | O15—H5 | 0.844 |
| C4—C5 | 1.380 (5) | O15—H13 | 0.832 |
| C4—H41 | 0.961 | K14—O9ii | 2.733 (3) |
| C5—S6 | 1.773 (3) | K14—O7iii | 2.736 (3) |
| C5—C10 | 1.382 (5) | K14—O15iii | 2.816 (3) |
| S6—O7 | 1.456 (3) | K14—O7iv | 2.834 (3) |
| S6—O8 | 1.452 (2) | K14—O9 | 2.934 (3) |
| S6—O9 | 1.442 (3) | K14—O15 | 2.937 (3) |
| C10—C11 | 1.383 (5) | K14—O8iv | 2.970 (3) |
| C10—H101 | 0.952 | K14—O7 | 3.211 (3) |
| C1i—C1—C2 | 111.4 (4) | O7—S6—O9 | 112.47 (18) |
| C1i—C1—C12 | 116.9 (4) | O8—S6—O9 | 114.94 (17) |
| C2—C1—C12 | 112.1 (3) | C5—C10—C11 | 119.9 (3) |
| C1i—C1—H11 | 104.1 | C5—C10—H101 | 119.6 |
| C2—C1—H11 | 104.9 | C11—C10—H101 | 120.5 |
| C12—C1—H11 | 106.2 | C2—C11—C10 | 121.4 (3) |
| C1—C2—C3 | 121.3 (3) | C2—C11—H111 | 119.0 |
| C1—C2—C11 | 121.1 (3) | C10—C11—H111 | 119.6 |
| C3—C2—C11 | 117.6 (3) | C1—C12—C13 | 114.2 (4) |
| C2—C3—C4 | 121.9 (3) | C1—C12—H121 | 109.5 |
| C2—C3—H31 | 117.9 | C13—C12—H121 | 108.1 |
| C4—C3—H31 | 120.2 | C1—C12—H122 | 106.9 |
| C3—C4—C5 | 119.1 (3) | C13—C12—H122 | 107.6 |
| C3—C4—H41 | 121.1 | H121—C12—H122 | 110.5 |
| C5—C4—H41 | 119.8 | C12—C13—H131 | 106.9 |
| C4—C5—S6 | 121.1 (2) | C12—C13—H132 | 109.2 |
| C4—C5—C10 | 120.0 (3) | H131—C13—H132 | 109.6 |
| S6—C5—C10 | 118.9 (3) | C12—C13—H133 | 109.4 |
| C5—S6—O7 | 104.86 (14) | H131—C13—H133 | 111.4 |
| C5—S6—O8 | 106.39 (14) | H132—C13—H133 | 110.4 |
| O7—S6—O8 | 110.82 (17) | H5—O15—H13 | 106.5 |
| C5—S6—O9 | 106.55 (15) |
| Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+1; (iv) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O15—H5···O8v | 0.84 | 2.00 | 2.790 (2) | 156 |
| Symmetry codes: (v) −x, −y+1, −z+1. |
| K14—O9i | 2.733 (3) | K14—O9 | 2.934 (3) |
| K14—O7ii | 2.736 (3) | K14—O15 | 2.937 (3) |
| K14—O15ii | 2.816 (3) | K14—O8iii | 2.970 (3) |
| K14—O7iii | 2.834 (3) | K14—O7 | 3.211 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O15—H5···O8iv | 0.84 | 2.00 | 2.790 (2) | 156 |
| Symmetry codes: (iv) −x, −y+1, −z+1. |
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The synthesis has been described by Torf & Khromov-Borisov (1961). Replacement of the two OH groups of the estrogen hexestrol molecule with two KSO3 groups results in the formation of the dipotassium salt of 4,4'-(1,2-diethyl-1,2-ethanediyl)bis(benzenesulfonic acid), also known as sygethin. Although the placement of carbon atoms in sygethin is very similar to hexestrol (Weeks et al., 1973) sygethin does not show estrogen-type activity (Svergun, 1979).
The crystal structure of the title compound has been determined. Fig. 1 illustrates the structure. The anion is located on a center of symmetry. The unit cell contains one sygethin anion, two potassium cations and two water molecules.
The packing diagram, Fig. 2, indicates that there are eight oxygen atoms coordinated to the potassium ion in a very distorted cubic geometry: six oxygen atoms are from four sygethin SO3 ions and two oxygen atoms are from the two water molecules. A hydrogen bond is formed by each water molecule and sygethin.