Hexaaqua­(5,7-dihydr­oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)calcium(II) 5,7-dihydr­oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonate trihydrate

Bin Liu; Bo-Lun Yang

doi:10.1107/S1600536808037586

. 2008 Nov 20;64(Pt 12):m1569–m1570. doi: 10.1107/S1600536808037586

Hexaaqua(5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)calcium(II) 5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonate trihydrate

Bin Liu ^a,^b,^*, Bo-Lun Yang ^a

PMCID: PMC2959999 PMID: 21581174

Abstract

In the title compound, [Ca(C₁₅H₉O₇S)(H₂O)₆](C₁₅H₉O₇S)·3H₂O, the Ca centre has a distorted decahedral geometry, coordinated by six O atoms from water molecules and one sulfonate O atom. The crystal structure is stabilized by aromatic π–π interactions, with centroid–centroid distances of 3.765 (5) and 3.896 (5) Å between the phenyl ring and the benzene ring of the chromene unit of neighbouring molecules. In addition, the stacked molecules exhibit inter- and intramolecular O—H⋯O hydrogen bonds, including the uncoordinated water molecules.

Related literature

For biological activity, see: Chan et al. (2000 ▶); Hiroyuki et al. (1996 ▶); Jiang et al. (2001 ▶); Lee et al. (1999 ▶); Shin et al. (1999 ▶); Zanoli et al. (2000 ▶). For related structures, see: Cote & Shimizu (2003 ▶); Li & Zhang (2008 ▶); Morin et al. (2000 ▶); Pusz et al. (2001 ▶); Zhang et al. (2004 ▶, 2006a ▶,b ▶).

Experimental

Crystal data

[Ca(C₁₅H₉O₇S)(H₂O)₆](C₁₅H₉O₇S)·3H₂O
M _r = 868.79
Triclinic,
a = 11.360 (2) Å
b = 12.390 (1) Å
c = 13.975 (2) Å
α = 95.136 (2)°
β = 102.167 (3)°
γ = 107.423 (2)°
V = 1809.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 296 (2) K
0.36 × 0.23 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.874, T _max = 0.947
9179 measured reflections
6299 independent reflections
4416 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.167
S = 1.04
6299 reflections
558 parameters
16 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037586/lx2072sup1.cif

e-64-m1569-sup1.cif^{(32.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037586/lx2072Isup2.hkl

e-64-m1569-Isup2.hkl^{(308.3KB, 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
O3—H3⋯O2	0.82	1.85	2.576 (4)	148
O4—H4⋯O5	0.82	1.82	2.579 (4)	153
O8—H8B⋯O17ⁱ	0.82 (4)	2.20 (3)	2.934 (4)	149 (4)
O8—H8A⋯O20ⁱⁱ	0.82 (3)	1.97 (3)	2.790 (4)	176 (5)
O9—H9B⋯O5	0.82 (4)	1.99 (4)	2.780 (4)	163 (5)
O9—H9A⋯O23ⁱⁱⁱ	0.83 (3)	1.92 (3)	2.743 (4)	175 (5)
O10—H10B⋯O20ⁱⁱ	0.82 (3)	2.13 (2)	2.874 (4)	151 (5)
O10—H10A⋯O22	0.82 (3)	1.90 (3)	2.715 (4)	171 (5)
O11—H11B⋯O6ⁱⁱⁱ	0.82 (3)	2.36 (3)	3.024 (4)	139 (4)
O11—H11A⋯O19	0.82 (4)	2.19 (4)	3.003 (4)	175 (5)
O12—H12B⋯O15^iv	0.81 (3)	1.98 (3)	2.771 (4)	165 (5)
O12—H12A⋯O21	0.82 (4)	1.88 (4)	2.695 (5)	177 (4)
O13—H13B⋯O3^v	0.82 (4)	2.05 (4)	2.867 (4)	174 (5)
O13—H13A⋯O23	0.82 (3)	2.00 (3)	2.819 (4)	173 (5)
O16—H16⋯O15	0.82	1.83	2.567 (4)	148
O17—H17⋯O18	0.82	1.80	2.556 (4)	153
O21—H21B⋯O18	0.82 (3)	2.05 (4)	2.870 (4)	176 (5)
O21—H21A⋯O22ⁱⁱ	0.82 (3)	2.01 (3)	2.826 (5)	173 (5)
O23—H23A⋯O2^vi	0.82 (4)	2.00 (4)	2.816 (4)	171 (5)
O23—H23B⋯O6	0.82 (4)	1.95 (4)	2.755 (4)	168 (5)
C12—H12⋯O11ⁱ	0.93	2.55	3.462 (5)	168
C20—H20⋯O8^vii	0.93	2.52	3.410 (5)	161

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

Acknowledgments

Support from the Natural Science Foundation of Shaanxi Province (grant No. 2005B01) is gratefully acknowledged.

supplementary crystallographic information

Comment

Chrysin (5,7-dihydroxyflavone), a naturally wide distributed flavonoid, has many different biological activities such as anti-oxidant (Chan et al., 2000), anti-virus (Lee et al., 1999), anti-diabetogenic activity (Shin et al., 1999), anti-anxiolytic effect (Zanoli et al., 2000). Sulfonates belong to an important class of organic compounds, particularly flavonoidsulfonates have many different biological activities (Hiroyuki et al., 1996; Jiang et al., 2001). Previously, two chrysinsulfonate derivatives have been prepared. Zhang et al. (2004, 2006a, 2006b) have synthesized chrysin-6-sulfonate and its derivates, such as [Ba(C₁₅H₉O₇S)₂]_n, [Zn(C₁₅H₈O₇S)(DMSO)]₂.H₂O and [{Ca(C₁₅H₈O₇S)(H₂O)(DMSO)}₃ {Ca(C₁₅H₈O₇S)(DMSO)₂}].4DMSO. Pusz et al. (2001) have reported chrysin-4'-sulfonate and its Ti⁴⁺, Mn²⁺ and Fe³⁺ complexes. On the other hand, the weak coordination nature of SO3^- makes its coordination mode very flexible and sensitive to the chemical environment (Cote & Shimizu, 2003). Here we report the crystal structure of the title compound (Fig. 1).

As shown in Fig. 1, the Ca atom is seven-coordinated by the six O atoms from water molecules and the one sulfonate O atom. The Ca—O bond lengths are in agreement with the corresponding values in [Ca(C₁₆H₁₂O₄)(H₂O)₆]. H₂O (Morin et al., 2000). The flavone skeleton is essentially planar, the bond lengths and angles are similar to those reported for other flavonesulfonates, [Co(H₂O)₆](C₁₆H₁₁O₇S)₂.4H₂O (Li & Zhang, 2008). The molecular packing (Fig. 2) is stabilized by two different aromatic π–π interactions within each stack of molecule; one between the phenyl ring (Cg1) and the benzene ring (Cg4ⁱⁱ) of the adjacent molecules {distance; 3.765 (5) Å}, and the other between the benzene ring (Cg2) and the phenyl ring (Cg3ⁱⁱ) of the neighbouring molecules {distance; 3.896 (5) Å} (Fig. 2; Cg1, Cg2, Cg3 and Cg4 are the centroids of the C1–C6 phenyl, the C10–C15 benzene, the C16–C21 phenyl and the C25–C30 benzene rings, respectively, symmetry code as in Fig. 2). Additionally, the crystal structure exhibits numerous inter- and intramolecular O—H···O hydrogen bonds (Fig. 1 & Hydrogen-bond geometry).

Experimental

5,7-Dihydroxyflavone (chrysin, 1.0 g, 3.9 mmol) was added slowly to concentrated sulfuric acid (6 ml) with stirring. The reaction was maintained at room temperature for 12 h. Then, it was poured into NaCl saturated aqueous solution (50 ml) and a yellow precipitate appeared. After 5 h, the precipitate was filtered and washed with NaCl saturated aqueous solution until the pH value of the filtrate was 7. It was dissolved in water (50 ml), and mixed with saturated CaCl₂ solution (10 ml). (I) was obtained after 24 h. It was recrystallized from an ethanol-water (1:1 v/v) solution. Colorless sheet-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent for about 3 d at room temperature (yield 78%).