Dipotassium 4,4′-(hexane-3,4-di­yl)bis­(benzene­sulfonate) dihydrate

Orola, L.; Veidis, M.V.; Belyakov, S.; Actins, A.

doi:10.1107/S160053680802120X

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1027

doi:10.1107/S160053680802120X

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Dipotassium 4,4′-(hexane-3,4-diyl)bis(benzenesulfonate) dihydrate

Liana Orola,^a Mikelis V. Veidis,^a ^* Sergey Belyakov ^b and Andris Actins ^a

^aUniversity of Latvia, Kr. Valdemara 48, Riga, LV 1013, Latvia, and ^bLatvian Institute of Organic Synthesis, Aizkraukles 21, Riga, LV 1006, Latvia
^*Correspondence e-mail: veidis@lu.lv

(Received 4 July 2008; accepted 8 July 2008; online 16 July 2008)

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.

Related literature

For the synthesis, see: Torf & Khromov-Borisov (1961 ). For general background, see: Svergun (1979 ). For a related structure, see: Weeks et al. (1973 ).

Experimental

Crystal data

2K⁺·C₁₈H₂₀O₆S₂²⁻·2H₂O
M_r = 255.36
Triclinic, $[P \overline 1]$
a = 5.8741 (5) Å
b = 6.5684 (5) Å
c = 15.2335 (14) Å
α = 84.272 (4)°
β = 83.768 (5)°
γ = 76.522 (6)°
V = 566.51 (8) Å³
Z = 1
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 298 K
0.27 × 0.19 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
4330 measured reflections
2576 independent reflections
1918 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.122
S = 0.89
1918 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 1.49 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected bond lengths (Å)

K14—O9ⁱ	2.733 (3)
K14—O7ⁱⁱ	2.736 (3)
K14—O15ⁱⁱ	2.816 (3)
K14—O7ⁱⁱⁱ	2.834 (3)
K14—O9	2.934 (3)
K14—O15	2.937 (3)
K14—O8ⁱⁱⁱ	2.970 (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.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O15—H5⋯O8^iv	0.84	2.00	2.790 (2)	156
Symmetry code: (iv) -x, -y+1, -z+1.

Data collection: COLLECT (Nonius, 2001 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO/SCALEPACK; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680802120X/cf2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802120X/cf2208Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For the synthesis, see: Torf & Khromov-Borisov (1961). For general background, see: Svergun (1979). For a related structure, see: Weeks et al. (1973).

Experimental top

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.

Computing details top

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).

Figures top

	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.]
	Fig. 2. Packing diagram of the title compound.

Dipotassium 4,4'-(hexane-3,4-diyl)bis(benzenesulfonate) dihydrate top

Crystal data top

2K⁺·C₁₈H₂₀O₆S₂²⁻·2H₂O	Z = 1
M_r = 255.36	F(000) = 266
Triclinic, P1	D_x = 1.497 Mg m⁻³ D_m = Mg m⁻³ D_m 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 = 1.4–27.4°
c = 15.2335 (14) Å	µ = 0.64 mm⁻¹
α = 84.272 (4)°	T = 298 K
β = 83.768 (5)°	Prism, colourless
γ = 76.522 (6)°	0.27 × 0.19 × 0.14 mm
V = 566.51 (8) Å³

Data collection top

Nonius KappaCCD diffractometer	1918 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.027
Graphite monochromator	θ_max = 27.4°, θ_min = 1.4°
ϕ and ω scans	h = −7→7
4330 measured reflections	k = −8→8
2576 independent reflections	l = −18→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.051	w = [1-(F_o-F_c)²/36σ²(F)]²/[53.8T₀(x) + 84.3T₁(x) + 51.6T₂(x) + 20.0T₃(x) + 5.48T₄(x)] where T_i are Chebychev polynomials and x = F_c/F_max
wR(F²) = 0.122	(Δ/σ)_max = 0.000280
S = 0.89	Δρ_max = 1.49 e Å⁻³
1918 reflections	Δρ_min = −0.42 e Å⁻³
137 parameters

Crystal data top

2K⁺·C₁₈H₂₀O₆S₂²⁻·2H₂O	γ = 76.522 (6)°
M_r = 255.36	V = 566.51 (8) Å³
Triclinic, P1	Z = 1
a = 5.8741 (5) Å	Mo Kα radiation
b = 6.5684 (5) Å	µ = 0.64 mm⁻¹
c = 15.2335 (14) Å	T = 298 K
α = 84.272 (4)°	0.27 × 0.19 × 0.14 mm
β = 83.768 (5)°

Data collection top

Nonius KappaCCD diffractometer	1918 reflections with I > 2σ(I)
4330 measured reflections	R_int = 0.027
2576 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 0.89	Δρ_max = 1.49 e Å⁻³
1918 reflections	Δρ_min = −0.42 e Å⁻³
137 parameters

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—O7^iv	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—O8^iv	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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O15—H5···O8^v	0.84	2.00	2.790 (2)	156

Symmetry code: (v) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	2K⁺·C₁₈H₂₀O₆S₂²⁻·2H₂O
M_r	255.36
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.8741 (5), 6.5684 (5), 15.2335 (14)
α, β, γ (°)	84.272 (4), 83.768 (5), 76.522 (6)
V (Å³)	566.51 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.27 × 0.19 × 0.14

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4330, 2576, 1918
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.122, 0.89
No. of reflections	1918
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.49, −0.42

Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997).

Selected bond lengths (Å) top

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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O15—H5···O8^iv	0.84	2.00	2.790 (2)	156

Symmetry code: (iv) −x, −y+1, −z+1.

Acknowledgements

Financial aid was provided by Latvia Science Council grant 05.1737.

References

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