Genistein-3'-sulfonic acid dihydrate.

IN THE TITLE COMPOUND [SYSTEMATIC NAME: 5-(5,7-dihydr-oxy-4-oxo-4H-chromen-yl)-2-hydroxy-benzene-sulfonic acid dihydrate], C(15)H(10)O(8)S·2H(2)O, the benzopyran-one ring is not coplanar with the phenyl ring, the dihedral angle between them being 41.35 (3)°. No H atom was placed on the sulphonic acid group because it was not possible to distinguish between the two S=O bonds and the S-O bond. In the crystal, the mol-ecules are linked by classical O-H⋯O and C-H⋯O intra- and inter-molecular hydrogen bonds and aromatic π-π stacking inter-actions [centroid-centroid distance of 3.4523 (14) Å between the 1, 4-pyran-one rings and the benzene rings, and 3.6337 (14) Å between the benzene rings] into a supra-molecular structure.

Related literature

Genistein is an isoflavone that can be extracted from plants such as soybean, trifolium, puerarin, see: Curnow et al. (1955 ▶); Kaufman et al. (1997 ▶). For its anti-tumour, anti-arteriosclerosis and anti-bone loss properties, see: Fritz et al. (1998 ▶); Zhu et al. (2006 ▶). It can also reduce plasma lipids and kill various cancer cells without damaging normal cells, see: Fanti et al. (1998 ▶); Lamartiniere (2000 ▶). It has poor solubility in water and fat (Suo et al., 2005 ▶). One effective way to increase the solubility of these compounds is to involve a sulfonate group, see: Kopacz (1981 ▶); Pusz et al. (2001 ▶); Xie et al. (2002 ▶).

Experimental

Crystal data

C15H10O8S·2H2O

M = 386.31

Triclinic,

a = 7.9100 (4) Å

b = 8.1977 (3) Å

c = 14.3431 (7) Å

α = 73.626 (3)°

β = 80.346 (3)°

γ = 65.498 (3)°

V = 810.61 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.20 × 0.20 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.952, T max = 0.988

7136 measured reflections

3736 independent reflections

2466 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.114

S = 0.95

3736 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.47 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014767/fl2244sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014767/fl2244Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H10O8S·2H2O	V = 810.61 (6) Å3
Mr = 386.31	Z = 2
Triclinic, P1	F(000) = 398
Hall symbol: -P 1	Dx = 1.579 Mg m−3
a = 7.9100 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1977 (3) Å	θ = 2.8–27.6°
c = 14.3431 (7) Å	µ = 0.26 mm−1
α = 73.626 (3)°	T = 296 K
β = 80.346 (3)°	Block, yellow
γ = 65.498 (3)°	0.20 × 0.20 × 0.05 mm

Bruker SMART APEXII CCD area-detector diffractometer	3736 independent reflections
Radiation source: fine-focus sealed tube	2466 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 27.6°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.952, Tmax = 0.988	k = −10→10
7136 measured reflections	l = −16→18

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 0.95	w = 1/[σ2(Fo2) + (0.0499P)2] where P = (Fo2 + 2Fc2)/3
3736 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.47 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.91573 (8)	0.62831 (8)	0.13396 (4)	0.02871 (17)
O1	0.3853 (2)	0.9816 (2)	0.33901 (11)	0.0349 (4)
O2	0.2966 (2)	1.1865 (2)	0.46121 (12)	0.0463 (5)
H2A	0.3371	1.1535	0.4101	0.056*
O3	0.0060 (2)	0.9940 (2)	0.76568 (11)	0.0441 (5)
H3A	0.0326	1.0699	0.7804	0.053*
O4	0.1972 (2)	0.62379 (19)	0.54241 (11)	0.0325 (4)
O5	0.7199 (2)	0.4397 (2)	0.05141 (12)	0.0483 (5)
H5A	0.8324	0.4128	0.0492	0.058*
C1	0.3351 (3)	0.8670 (3)	0.40347 (15)	0.0263 (5)
C2	0.2545 (3)	0.9026 (3)	0.49667 (15)	0.0246 (5)
C3	0.2355 (3)	1.0616 (3)	0.52404 (16)	0.0296 (5)
C4	0.1563 (3)	1.0929 (3)	0.61293 (17)	0.0339 (6)
H4A	0.1465	1.1976	0.6303	0.041*
C5	0.0900 (3)	0.9663 (3)	0.67758 (16)	0.0305 (5)
C6	0.1018 (3)	0.8113 (3)	0.65325 (16)	0.0299 (5)
H6A	0.0550	0.7290	0.6959	0.036*
C7	0.1848 (3)	0.7812 (3)	0.56408 (16)	0.0263 (5)
C8	0.2829 (3)	0.5863 (3)	0.45676 (16)	0.0313 (5)
H8A	0.2944	0.4762	0.4448	0.038*
C9	0.3528 (3)	0.6939 (3)	0.38735 (15)	0.0261 (5)
C10	0.4469 (3)	0.6336 (3)	0.29699 (15)	0.0265 (5)
C11	0.3792 (3)	0.5469 (3)	0.25092 (17)	0.0352 (6)
H11A	0.2693	0.5304	0.2753	0.042*
C12	0.4730 (3)	0.4846 (3)	0.16923 (18)	0.0392 (6)
H12A	0.4249	0.4277	0.1391	0.047*
C13	0.6385 (3)	0.5062 (3)	0.13165 (16)	0.0317 (5)
C14	0.7058 (3)	0.5965 (3)	0.17563 (15)	0.0250 (5)
C15	0.6094 (3)	0.6585 (3)	0.25784 (15)	0.0259 (5)
H15A	0.6554	0.7181	0.2872	0.031*
O1W	0.6658 (3)	0.1139 (2)	0.02597 (15)	0.0646 (6)
H3	0.7677	0.0288	0.0470	0.078*
H4	0.6800	0.2140	0.0191	0.078*
O2W	0.3261 (3)	0.0875 (3)	0.13170 (15)	0.0775 (7)
H1	0.4261	0.0988	0.1045	0.093*
H2	0.2363	0.1863	0.1398	0.093*
O6A	0.9142 (16)	0.6736 (12)	0.0261 (8)	0.0346 (14)	0.54
O7A	1.067 (2)	0.456 (2)	0.1681 (9)	0.043 (2)	0.54
O8A	0.8999 (11)	0.7821 (10)	0.1651 (4)	0.0369 (13)	0.54
O6B	0.899 (2)	0.7323 (15)	0.0381 (10)	0.067 (3)	0.46
O7B	1.059 (2)	0.450 (3)	0.1480 (12)	0.069 (5)	0.46
O8B	0.9427 (13)	0.7255 (13)	0.2012 (5)	0.061 (3)	0.46

	U11	U22	U33	U12	U13	U23
S1	0.0283 (3)	0.0327 (3)	0.0301 (3)	−0.0149 (3)	0.0043 (2)	−0.0138 (3)
O1	0.0453 (10)	0.0311 (9)	0.0315 (9)	−0.0208 (8)	0.0095 (7)	−0.0101 (7)
O2	0.0694 (13)	0.0418 (10)	0.0434 (11)	−0.0385 (10)	0.0200 (9)	−0.0212 (8)
O3	0.0580 (12)	0.0550 (11)	0.0329 (10)	−0.0313 (10)	0.0116 (8)	−0.0246 (8)
O4	0.0455 (10)	0.0261 (8)	0.0295 (9)	−0.0185 (8)	0.0071 (7)	−0.0101 (7)
O5	0.0406 (10)	0.0809 (13)	0.0468 (11)	−0.0340 (10)	0.0169 (8)	−0.0454 (10)
C1	0.0241 (11)	0.0258 (11)	0.0273 (12)	−0.0086 (10)	−0.0008 (9)	−0.0061 (10)
C2	0.0267 (11)	0.0224 (11)	0.0249 (12)	−0.0098 (9)	0.0003 (9)	−0.0068 (9)
C3	0.0311 (12)	0.0291 (12)	0.0326 (13)	−0.0152 (10)	0.0024 (10)	−0.0105 (10)
C4	0.0380 (13)	0.0367 (13)	0.0367 (14)	−0.0181 (11)	0.0011 (10)	−0.0197 (11)
C5	0.0292 (12)	0.0394 (13)	0.0235 (12)	−0.0107 (11)	0.0007 (9)	−0.0133 (10)
C6	0.0332 (13)	0.0296 (12)	0.0269 (12)	−0.0140 (10)	0.0017 (9)	−0.0056 (10)
C7	0.0267 (12)	0.0236 (11)	0.0287 (12)	−0.0085 (10)	−0.0020 (9)	−0.0080 (10)
C8	0.0374 (13)	0.0267 (12)	0.0318 (13)	−0.0123 (11)	0.0066 (10)	−0.0154 (10)
C9	0.0250 (11)	0.0253 (11)	0.0280 (12)	−0.0090 (10)	0.0009 (9)	−0.0091 (10)
C10	0.0275 (11)	0.0263 (11)	0.0253 (12)	−0.0090 (10)	0.0012 (9)	−0.0093 (9)
C11	0.0296 (13)	0.0463 (14)	0.0379 (14)	−0.0203 (12)	0.0054 (10)	−0.0180 (12)
C12	0.0363 (14)	0.0562 (16)	0.0432 (15)	−0.0268 (13)	0.0056 (11)	−0.0299 (13)
C13	0.0318 (13)	0.0403 (13)	0.0272 (12)	−0.0145 (11)	0.0030 (9)	−0.0163 (11)
C14	0.0239 (11)	0.0253 (11)	0.0257 (12)	−0.0096 (9)	−0.0003 (9)	−0.0064 (9)
C15	0.0257 (11)	0.0262 (11)	0.0272 (12)	−0.0084 (10)	−0.0033 (9)	−0.0101 (9)
O1W	0.0601 (13)	0.0449 (11)	0.0873 (16)	−0.0203 (10)	−0.0079 (11)	−0.0116 (11)
O2W	0.0639 (15)	0.0834 (15)	0.0737 (16)	−0.0237 (13)	0.0042 (11)	−0.0139 (12)
O6A	0.036 (2)	0.045 (3)	0.023 (2)	−0.015 (3)	0.0032 (16)	−0.011 (2)
O7A	0.029 (3)	0.051 (6)	0.043 (3)	−0.018 (3)	−0.009 (2)	0.005 (3)
O8A	0.048 (3)	0.048 (3)	0.035 (3)	−0.031 (2)	0.003 (2)	−0.024 (2)
O6B	0.056 (5)	0.095 (9)	0.041 (6)	−0.041 (6)	0.002 (4)	0.014 (5)
O7B	0.025 (5)	0.032 (5)	0.129 (13)	0.000 (4)	0.019 (6)	−0.018 (7)
O8B	0.051 (5)	0.123 (8)	0.053 (5)	−0.058 (5)	0.022 (3)	−0.065 (5)

S1—O6B	1.394 (14)	C4—C5	1.399 (3)
S1—O8A	1.404 (7)	C4—H4A	0.9300
S1—O7B	1.412 (16)	C5—C6	1.374 (3)
S1—O7A	1.438 (14)	C6—C7	1.375 (3)
S1—O6A	1.487 (11)	C6—H6A	0.9300
S1—O8B	1.501 (8)	C8—C9	1.342 (3)
S1—C14	1.766 (2)	C8—H8A	0.9300
O1—C1	1.262 (2)	C9—C10	1.487 (3)
O2—C3	1.356 (3)	C10—C15	1.385 (3)
O2—H2A	0.8207	C10—C11	1.389 (3)
O3—C5	1.358 (2)	C11—C12	1.384 (3)
O3—H3A	0.8205	C11—H11A	0.9300
O4—C8	1.350 (2)	C12—C13	1.392 (3)
O4—C7	1.372 (2)	C12—H12A	0.9300
O5—C13	1.360 (2)	C13—C14	1.390 (3)
O5—H5A	0.8206	C14—C15	1.395 (3)
C1—C2	1.435 (3)	C15—H15A	0.9300
C1—C9	1.447 (3)	O1W—H3	0.8508
C2—C7	1.401 (3)	O1W—H4	0.8502
C2—C3	1.408 (3)	O2W—H1	0.8500
C3—C4	1.366 (3)	O2W—H2	0.8500
O8A—S1—O7A	117.5 (7)	C6—C5—C4	121.3 (2)
O8A—S1—O6A	110.1 (4)	C5—C6—C7	118.1 (2)
O7A—S1—O6A	110.5 (6)	C5—C6—H6A	121.0
O8A—S1—C14	105.6 (3)	C7—C6—H6A	121.0
O7A—S1—C14	107.8 (7)	O4—C7—C6	116.80 (19)
O6A—S1—C14	104.3 (5)	O4—C7—C2	120.09 (19)
O6B—S1—O7B	115.3 (8)	C6—C7—C2	123.1 (2)
O6B—S1—O8B	112.3 (5)	C9—C8—O4	125.7 (2)
O7B—S1—O8B	107.7 (8)	C9—C8—H8A	117.2
O6B—S1—C14	108.5 (6)	O4—C8—H8A	117.2
O8A—S1—C14	105.6 (3)	C8—C9—C1	118.4 (2)
O7B—S1—C14	106.3 (9)	C8—C9—C10	119.97 (19)
O7A—S1—C14	107.8 (7)	C1—C9—C10	121.67 (18)
O6A—S1—C14	104.3 (5)	C15—C10—C11	118.0 (2)
O8B—S1—C14	106.2 (4)	C15—C10—C9	120.2 (2)
C3—O2—H2A	109.4	C11—C10—C9	121.7 (2)
C5—O3—H3A	109.5	C12—C11—C10	120.9 (2)
C8—O4—C7	118.66 (16)	C12—C11—H11A	119.5
C13—O5—H5A	109.4	C10—C11—H11A	119.5
O1—C1—C2	121.64 (19)	C11—C12—C13	120.7 (2)
O1—C1—C9	122.13 (19)	C11—C12—H12A	119.6
C2—C1—C9	116.23 (18)	C13—C12—H12A	119.6
C7—C2—C3	116.69 (19)	O5—C13—C14	124.9 (2)
C7—C2—C1	120.75 (19)	O5—C13—C12	116.1 (2)
C3—C2—C1	122.53 (19)	C14—C13—C12	119.0 (2)
O2—C3—C4	119.2 (2)	C13—C14—C15	119.4 (2)
O2—C3—C2	119.6 (2)	C13—C14—S1	122.28 (16)
C4—C3—C2	121.2 (2)	C15—C14—S1	118.27 (17)
C3—C4—C5	119.6 (2)	C10—C15—C14	121.9 (2)
C3—C4—H4A	120.2	C10—C15—H15A	119.1
C5—C4—H4A	120.2	C14—C15—H15A	119.1
O3—C5—C6	117.1 (2)	H3—O1W—H4	105.1
O3—C5—C4	121.6 (2)	H1—O2W—H2	116.1

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H1···O1W	0.85	2.07	2.915 (3)	173
O2W—H2···O7Ai	0.85	2.17	2.999 (15)	165
O2W—H2···O6Aii	0.85	2.58	2.903 (13)	104
O2—H2A···O1	0.82	1.85	2.580 (2)	148
O1W—H3···O8Aiii	0.85	2.23	2.968 (7)	146
O3—H3A···O8Aiv	0.82	1.89	2.705 (8)	171
O1W—H4···O5	0.85	2.18	3.000 (2)	162
O5—H5A···O6A	0.82	2.40	2.835 (12)	114
O5—H5A···O6Av	0.82	2.05	2.784 (14)	148
C6—H6A···O7Avi	0.93	2.44	3.356 (15)	169
C8—H8A···O2iii	0.93	2.31	3.217 (3)	164
C15—H15A···O1	0.93	2.52	2.944 (3)	108
C15—H15A···O8A	0.93	2.50	2.868 (9)	104

Cg	Cg	α	DCC	τ
Cg1	Cg2i	1.38	3.4524 (14)	15.63
Cg2	Cg2i	0.03	3.6336 (14)	24.54

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H1⋯O1W	0.85	2.07	2.915 (3)	173
O2W—H2⋯O7Ai	0.85	2.17	2.999 (15)	165
O2W—H2⋯O6Aii	0.85	2.58	2.903 (13)	104
O2—H2A⋯O1	0.82	1.85	2.580 (2)	148
O1W—H3⋯O8Aiii	0.85	2.23	2.968 (7)	146
O3—H3A⋯O8Aiv	0.82	1.89	2.705 (8)	171
O1W—H4⋯O5	0.85	2.18	3.000 (2)	162
O5—H5A⋯O6A	0.82	2.40	2.835 (12)	114
O5—H5A⋯O6Av	0.82	2.05	2.784 (14)	148
C6—H6A⋯O7Avi	0.93	2.44	3.356 (15)	169
C8—H8A⋯O2iii	0.93	2.31	3.217 (3)	164

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .