Genistein-3′-sulfonic acid dihydrate

Chang-Peng Zhang; Hao Ni; Hai-Yan Tu; Yong-Rong Xie; Rui-Qing Yang

doi:10.1107/S1600536809014767

. 2009 Apr 30;65(Pt 5):o1137–o1138. doi: 10.1107/S1600536809014767

Genistein-3′-sulfonic acid dihydrate

Chang-Peng Zhang ^a, Hao Ni ^a, Hai-Yan Tu ^a, Yong-Rong Xie ^a,^*, Rui-Qing Yang ^a

PMCID: PMC2977809 PMID: 21583946

Abstract

In the title compound [systematic name: 5-(5,7-dihydroxy-4-oxo-4H-chromenyl)-2-hydroxybenzenesulfonic acid dihydrate], C₁₅H₁₀O₈S·2H₂O, the benzopyranone 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 molecules are linked by classical O—H⋯O and C—H⋯O intra- and intermolecular hydrogen bonds and aromatic π–π stacking interactions [centroid–centroid distance of 3.4523 (14) Å between the 1, 4-pyranone rings and the benzene rings, and 3.6337 (14) Å between the benzene rings] into a supramolecular 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 _r = 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
Δρ_max = 0.52 e Å⁻³
Δρ_min = −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 ▶).

Supplementary Material

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

e-65-o1137-sup1.cif^{(18.8KB, cif)}

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

e-65-o1137-Isup2.hkl^{(183.2KB, hkl)}

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

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⋯O8A^iv	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⋯O6A^v	0.82	2.05	2.784 (14)	148
C6—H6A⋯O7A^vi	0.93	2.44	3.356 (15)	169
C8—H8A⋯O2ⁱⁱⁱ	0.93	2.31	3.217 (3)	164

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

Acknowledgments

The author thank the Natural Science Foundation of China (No. 20861001), the Natural Science Foundation of Jiangxi Province (No. 0620007), the Jiangxi Provincial Education Foundation (20060237) and the Gannan Normal University Foundation (No. 200409).

supplementary crystallographic information

Comment

Genistein is an isoflavone that can be extracted from plants such as soybean, trifolium, puerarin (Curnow et al. 1955; Kaufman et al., 1997). It has physiological functions of anti-tumour, anti-arteriosclerosis, anti-bone loss (Fritz et al., 1998; Zhu et al., 2006). It can also reduce plasma lipids and kill various cancer cells without damaging normal cells (Fanti et al., 1998; Lamartiniere, 2000). Nevertheless, its medical applications are restricted because of its 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 (Kopacz, 1981; Pusz et al., 2001; Xie et al. 2002).

We present here the structure of (I, Fig. 1), a new derivative of Genistein. In (I) the molecules are linked by classic O—H···O and C—H···O intra- and intermolecular hydrogen bonds (Table 1). Adjacent benzopyranone rings are aligned in a parallel and alternatively inverse fashion, with a centroid-centroid distance of 3.4523 (14)Å between 1, 4-pyranone rings and benzene rings, and 3.6337 (14)Å between the benzene rings (Table 2), indicating significant stacking interactions that form columns running along the a axis. The hydrogen bonding and π-π stacking interactions extend the structure into a 3-D supramolecular structure (Fig. 2 and Fig. 3).

Experimental

In a 100 ml flask are placed 40 ml 98% sulfuric acid and 10 g (37 mmol) genistein with stirrer. The resulting mixture is stirred at room temperature for 6 h. The reaction mixture is carefully diluted by addition of 40 ml ice water. The resulting yellow solid is filtered, and recrystallized from 50 ml of 90% acetonitrile to give 9.1–11 g (70–85%) of the title compound yellow crystals.