Poly[(μ-5,7-dihydr­oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)potassium(I)]

Liu, B.; Yang, B.-L.

doi:10.1107/S1600536808041779

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m66-m67

doi:10.1107/S1600536808041779

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Poly[(μ-5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)potassium(I)]

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

^aDepartment of Chemical Engineering, Xi'an Jiaotong University, Xi'an 710049, People's Republic of China, and ^bDepartment of Chemistry, Xianyang Normal University, Xianyang 712000, People's Republic of China
^*Correspondence e-mail: liubin1958@126.com

(Received 6 November 2008; accepted 9 December 2008; online 13 December 2008)

In the polymeric title compound, [K(C₁₅H₉O₇S)]_n, the potassium cation is five-coordinated by four sulfonate O atoms and one carbonyl O atom. Two intramolecular O—H⋯O hydrogen bonds stabilize the conformation of the anion. The polymeric three-dimensional supramolecular architecture is formed via coordination interactions and π–π stacking interactions involving centrosymmetrically related pyrone rings, with a centroid–centroid separation of 3.513 (2) Å.

Related literature

For biological activities of flavonoids, see: Aljancic et al. (1999 ); Habtemariam (1997 ); Knekt et al. (1997 ); Ko et al. (1998 ); Nkengfack et al. (1994 ); Sakaguchi et al. (1992 ). For related structures, see: Benedict et al. (2004 ); Li & Zhang (2008 ); Wang & Zhang (2005a ,b ); Zhang & Wang (2005a ,b ).

Experimental

Crystal data

[K(C₁₅H₉O₇S)]
M_r = 372.38
Orthorhombic, P c c n
a = 19.0846 (19) Å
b = 20.6555 (19) Å
c = 7.5148 (7) Å
V = 2962.3 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 296 (2) K
0.37 × 0.20 × 0.13 mm

Data collection

Bruker SMART-1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.825, T_max = 0.933
13998 measured reflections
2637 independent reflections
1746 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.152
S = 1.02
2637 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected bond lengths (Å)

K1—O5ⁱ	2.674 (2)
K1—O6ⁱⁱ	2.754 (2)
K1—O7ⁱⁱⁱ	2.655 (3)
K1—O3^iv	2.642 (2)
K1—O6	2.756 (3)
Symmetry codes: (i) x, y, z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O7	0.82	1.84	2.588 (4)	152
O2—H2⋯O3	0.82	1.87	2.604 (4)	148
Symmetry codes: .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041779/rz2268sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041779/rz2268Isup2.hkl

checkCIF report

Comment top

The biological properties of flavonoids (2-phenylbenzo-γ-pyrone derivatives) are well known (Sakaguchi et al., 1992; Nkengfack et al., 1994; Habtemariam, 1997; Knekt et al., 1997; Ko et al., 1998; Aljancic et al., 1999). The main problem that these compounds present for their use in biological experiments is their poor solubility in water. To overcome this problem, many flavonoidsulfonate derivatives have been synthesized, for example [Ni(H₂O)₆](C₁₇H₁₃O₇S)₂.8H₂O (Zhang & Wang, 2005a), [Sr(H₂O)₇(C₁₆H₁₁O₄SO₃)][C₁₆H₁₁O₄SO₃].6H₂O (Zhang & Wang, 2005b), [Mg(H₂O)₆](C₁₉H₁₇O₄SO₃)₂].8H₂O and [Zn(H₂O)₆](C₁₉H₁₇O₄SO₃)₂].8H₂O (Wang & Zhang, 2005a) and [Co(H₂O)₆](C₁₉H₁₇O₄SO₃)₂.8H₂O (Wang & Zhang, 2005b). Against this background, we report here the solid-state characterization of the potassium salt of 5,7-dihydroxyflavone-8-sulfonate.

The asymmetric unit of title compound consists of one potassium(I) cation and one 5,7-dihydroxyflavone-8-sulfonate anion (Fig. 1). The cation has a distorted coordination geometry and is coordinated by four sulfonate O atoms (O5ⁱ, O6, O6ⁱⁱ, and O7ⁱⁱⁱ; symmetry codes: (i) x, y, z + 1; (ii) x, -y + 1/2, z + 1/2; (iii) -x + 1/2, y, z + 1/2) and one carbonyl O atom (O3^iv; symmetry code: (iv) -x, -y + 1, -z + 1). The K—O bond distances (Table 1) are in agreement with those found in K⁺.C₁₆H₁₁O₈^-.2H₂O (Benedict et al., 2004). The flavone skeleton presents the same structure of a corresponding flavonesulfonate ligand reported previously (Li & Zhang, 2008) and is stabilized by intramolecular hydrogen bonds, with O1—H1···O7 = 2.588 (4) Å and O2—H2···O3 = 2.640 (4) Å (Table 2).

As shown in Fig. 2, K1^vi (symmetry code: (vi) x, -y + 1/2, z - 1/2) and K1^vii (symmetry code: (vii) -x + 1/2, y, z - 1/2) coordinate with O6 and O7^viii (symmetry code: (viii) -x + 1/2, -y + 1/2, z) and O6^viii and O7, respectively, resulting in a centrosymmetric eight-membered chelate ring that is non-planar. Coordination bonds K1^vi–O3^ix (symmetry code: (ix) -x, y - 1/2, -z + 1/2) and K1^vii–O3^x (symmetry code: (x) x + 1/2, -y + 1, -z + 1/2) link the flavone skeletons [C1—C15/O4]^ix and [C1—C15/O4]^x and the eight-membered ring together to form a two-dimensional sheet-like structure in the ab plane. Another eight-membered chelate ring is built up by O6ⁱⁱ, S1ⁱⁱ, O7ⁱⁱ, K1^viii, O6ⁱⁱⁱ, S1ⁱⁱⁱ, O7ⁱⁱⁱ and K1. Two adjacent eight-membered rings are further linked into a one-dimensional polyion chain along the c axis by the coordination bonds K1–O6, K1^vii–O5ⁱⁱⁱ, K1^viii–O6^viii and K1^vi–O5ⁱⁱ (Fig. 3). Additionally, π···π stacking interactions (Fig. 2) between centrosymmetrically related pyrone rings may be effective in the stabilization of the three-dimensional polymeric structure, with a centroid-centroid distance of 3.513 (2) Å, a perpendicular interplanar distance of 3.342 (3) Å and a centroid···centroid offset of 1.084 (2) Å.

Related literature top

For biological activities of flavonoids, see: Aljancic et al. (1999); Habtemariam (1997); Knekt et al. (1997); Ko et al. (1998); Nkengfack et al. (1994); Sakaguchi et al. (1992). For related structures, see: Benedict et al. (2004); Li & Zhang (2008); Wang & Zhang (2005a,b); Zhang & Wang (2005a,b).

Experimental top

5,7-dihydroxyflavone (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, the mixture was poured into a KCl saturated aqueous solution (50 ml) and a yellow precipitate appeared. After 5 h, the precipitate was filtered and washed with a KCl saturated aqueous solution until the pH value of the filtrate was 7. The solid product was recrystallized from an ethanol-water (1:1 v/v) solution. Colourless plate-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent for about 4 d at room temperature (yield 83%).

Computing details top

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

Figures top

	Fig. 1. The coordination environment of the potassium(I) cation in the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Intramolecular hydrogen bonds are shown as dashed lines. Symmetry codes: (i) x, y, z + 1; (ii) x, -y + 1/2, z + 1/2; (iii) -x + 1/2, y, z + 1/2; (iv) -x, -y + 1, -z + 1.
	Fig. 2. Packing diagram of the title compound viewed along the c axis, showing the sheet-like structure in the ab plane. The dashed line indicates the π–π stacking interaction. Cg1 is the centroid of the pyrone ring. Symmetry codes: (vi) x, -y + 1/2, z - 1/2; (vii) -x + 1/2, y, z - 1/2; (viii) -x + 1/2, -y + 1/2, z; (ix) -x, y - 1/2, -z + 1/2; (x) x + 1/2, -y + 1, -z + 1/2; (xi) -x, -y + 1, -z.
	Fig. 3. The one-dimensional polyion chain along the c axis in the title compound. Symmetry codes: (ii) x, -y + 1/2, z + 1/2; (iii) -x + 1/2, y, z + 1/2; (vi) x, -y + 1/2, z - 1/2; (vii) -y + 1/2, y, z - 1/2; (viii) -x + 1/2, -y + 1/2, z.

Poly[(µ-5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)potassium(I)] top

Crystal data top

[K(C₁₅H₉O₇S)]	F(000) = 1520
M_r = 372.38	D_x = 1.670 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 2056 reflections
a = 19.0846 (19) Å	θ = 2.9–20.9°
b = 20.6555 (19) Å	µ = 0.54 mm⁻¹
c = 7.5148 (7) Å	T = 296 K
V = 2962.3 (5) Å³	Plate, colourless
Z = 8	0.37 × 0.20 × 0.13 mm

Data collection top

Bruker SMART-1000 CCD area-detector diffractometer	2637 independent reflections
Radiation source: fine-focus sealed tube	1746 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −21→22
T_min = 0.825, T_max = 0.933	k = −24→22
13998 measured reflections	l = −7→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.091P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2637 reflections	Δρ_max = 0.26 e Å⁻³
220 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: none

Crystal data top

[K(C₁₅H₉O₇S)]	V = 2962.3 (5) Å³
M_r = 372.38	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 19.0846 (19) Å	µ = 0.54 mm⁻¹
b = 20.6555 (19) Å	T = 296 K
c = 7.5148 (7) Å	0.37 × 0.20 × 0.13 mm

Data collection top

Bruker SMART-1000 CCD area-detector diffractometer	2637 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1746 reflections with I > 2σ(I)
T_min = 0.825, T_max = 0.933	R_int = 0.049
13998 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.02	Δρ_max = 0.26 e Å⁻³
2637 reflections	Δρ_min = −0.29 e Å⁻³
220 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
K1	0.13853 (4)	0.30967 (3)	0.70530 (10)	0.0614 (3)
S1	0.15766 (5)	0.35454 (4)	0.23290 (12)	0.0609 (3)
O1	0.24816 (13)	0.46137 (12)	0.4226 (4)	0.0808 (8)
H1	0.2561	0.4241	0.3913	0.121*
O2	0.07320 (14)	0.61774 (10)	0.4594 (4)	0.0757 (8)
H2	0.0318	0.6235	0.4351	0.114*
O3	−0.04849 (13)	0.59352 (11)	0.3174 (3)	0.0681 (7)
O4	0.02313 (11)	0.41527 (10)	0.1793 (3)	0.0518 (6)
O5	0.14317 (13)	0.34558 (12)	0.0469 (3)	0.0711 (7)
O6	0.11604 (17)	0.31214 (11)	0.3432 (3)	0.0830 (8)
O7	0.23185 (16)	0.34965 (14)	0.2716 (4)	0.1005 (11)
C1	0.06796 (17)	0.45769 (15)	0.2611 (4)	0.0483 (8)
C2	0.13557 (17)	0.43436 (15)	0.2928 (4)	0.0510 (8)
C3	0.18152 (19)	0.47689 (16)	0.3815 (4)	0.0587 (8)
C4	0.15971 (19)	0.53813 (16)	0.4343 (5)	0.0637 (9)
H4	0.1910	0.5653	0.4928	0.076*
C5	0.09334 (19)	0.55884 (15)	0.4016 (4)	0.0574 (8)
C6	0.04475 (17)	0.51880 (14)	0.3107 (4)	0.0494 (8)
C7	−0.02559 (19)	0.53857 (15)	0.2717 (4)	0.0555 (9)
C8	−0.06835 (18)	0.49192 (16)	0.1810 (4)	0.0563 (8)
H8	−0.1140	0.5029	0.1495	0.068*
C9	−0.04401 (17)	0.43304 (15)	0.1409 (4)	0.0515 (8)
C10	−0.08112 (18)	0.38009 (16)	0.0517 (4)	0.0571 (8)
C11	−0.1517 (2)	0.3838 (2)	0.0188 (6)	0.0862 (13)
H11	−0.1761	0.4205	0.0549	0.103*
C12	−0.1872 (3)	0.3350 (2)	−0.0658 (8)	0.1055 (16)
H12	−0.2352	0.3384	−0.0857	0.127*
C13	−0.1515 (3)	0.2812 (2)	−0.1205 (6)	0.0930 (14)
H13	−0.1751	0.2485	−0.1806	0.112*
C14	−0.0811 (3)	0.27500 (18)	−0.0878 (6)	0.0805 (12)
H14	−0.0572	0.2380	−0.1237	0.097*
C15	−0.0457 (2)	0.32438 (16)	−0.0007 (4)	0.0654 (9)
H15	0.0019	0.3202	0.0229	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K1	0.0902 (6)	0.0465 (5)	0.0474 (5)	0.0031 (3)	−0.0002 (4)	−0.0003 (3)
S1	0.0824 (7)	0.0503 (5)	0.0499 (6)	0.0108 (4)	−0.0088 (4)	−0.0111 (4)
O1	0.0802 (18)	0.0717 (17)	0.0906 (19)	0.0055 (13)	−0.0169 (15)	−0.0260 (15)
O2	0.110 (2)	0.0437 (13)	0.0731 (18)	0.0056 (13)	−0.0029 (16)	−0.0139 (12)
O3	0.0923 (18)	0.0503 (14)	0.0618 (15)	0.0184 (12)	0.0040 (12)	−0.0021 (11)
O4	0.0652 (14)	0.0425 (12)	0.0477 (13)	−0.0009 (10)	0.0000 (10)	−0.0024 (10)
O5	0.0899 (17)	0.0801 (17)	0.0432 (15)	0.0097 (13)	−0.0021 (11)	−0.0177 (12)
O6	0.144 (2)	0.0461 (14)	0.0583 (15)	0.0019 (14)	0.0097 (16)	0.0017 (12)
O7	0.089 (2)	0.089 (2)	0.124 (3)	0.0313 (16)	−0.0417 (18)	−0.0468 (17)
C1	0.065 (2)	0.0459 (18)	0.0340 (17)	−0.0041 (14)	0.0040 (14)	0.0003 (13)
C2	0.068 (2)	0.0476 (18)	0.0368 (17)	0.0016 (15)	−0.0004 (15)	−0.0012 (14)
C3	0.074 (2)	0.0527 (19)	0.050 (2)	−0.0003 (17)	−0.0002 (17)	−0.0027 (16)
C4	0.082 (3)	0.050 (2)	0.059 (2)	−0.0092 (17)	−0.0038 (18)	−0.0100 (17)
C5	0.084 (2)	0.0445 (18)	0.0434 (19)	−0.0014 (16)	0.0025 (17)	−0.0013 (15)
C6	0.069 (2)	0.0425 (17)	0.0366 (17)	0.0021 (15)	0.0032 (15)	0.0009 (13)
C7	0.083 (2)	0.0437 (18)	0.0395 (17)	0.0045 (16)	0.0111 (16)	0.0056 (14)
C8	0.067 (2)	0.055 (2)	0.047 (2)	0.0026 (16)	0.0066 (16)	0.0026 (15)
C9	0.063 (2)	0.0546 (19)	0.0368 (17)	−0.0023 (16)	0.0067 (15)	0.0058 (14)
C10	0.067 (2)	0.056 (2)	0.048 (2)	−0.0070 (16)	0.0021 (16)	0.0012 (16)
C11	0.080 (3)	0.080 (3)	0.099 (3)	−0.005 (2)	−0.006 (2)	−0.021 (3)
C12	0.081 (3)	0.096 (3)	0.139 (5)	−0.013 (3)	−0.012 (3)	−0.021 (3)
C13	0.106 (4)	0.088 (3)	0.085 (3)	−0.039 (3)	−0.015 (3)	−0.006 (3)
C14	0.116 (4)	0.057 (2)	0.069 (3)	−0.015 (2)	0.002 (2)	−0.0078 (19)
C15	0.085 (3)	0.059 (2)	0.052 (2)	−0.0076 (19)	−0.0020 (18)	0.0029 (17)

Geometric parameters (Å, º) top

K1—O5ⁱ	2.674 (2)	C1—C2	1.398 (4)
K1—O6ⁱⁱ	2.754 (2)	C2—C3	1.409 (5)
K1—O7ⁱⁱⁱ	2.655 (3)	C3—C4	1.389 (5)
K1—O3^iv	2.642 (2)	C4—C5	1.359 (5)
K1—O6	2.756 (3)	C4—H4	0.9300
K1—S1ⁱⁱ	3.4177 (12)	C5—C6	1.418 (4)
S1—O5	1.437 (2)	C6—C7	1.433 (5)
S1—O6	1.444 (3)	C7—C8	1.435 (5)
S1—O7	1.449 (3)	C8—C9	1.336 (4)
S1—C2	1.760 (3)	C8—H8	0.9300
O1—C3	1.347 (4)	C9—C10	1.466 (4)
O1—H1	0.8200	C10—C11	1.371 (5)
O2—C5	1.348 (4)	C10—C15	1.391 (5)
O2—H2	0.8200	C11—C12	1.372 (6)
O3—C7	1.264 (4)	C11—H11	0.9300
O3—K1^iv	2.642 (2)	C12—C13	1.366 (6)
O4—C9	1.364 (4)	C12—H12	0.9300
O4—C1	1.370 (4)	C13—C14	1.372 (6)
O5—K1^v	2.674 (2)	C13—H13	0.9300
O6—K1^vi	2.754 (2)	C14—C15	1.387 (5)
O7—K1^vii	2.655 (3)	C14—H14	0.9300
C1—C6	1.389 (4)	C15—H15	0.9300

O3^iv—K1—O7ⁱⁱⁱ	112.50 (9)	C5—O2—H2	109.5
O3^iv—K1—O5ⁱ	82.73 (7)	C7—O3—K1^iv	152.5 (2)
O7ⁱⁱⁱ—K1—O5ⁱ	72.70 (8)	C9—O4—C1	120.6 (2)
O3^iv—K1—O6ⁱⁱ	127.89 (9)	S1—O5—K1^v	167.47 (15)
O7ⁱⁱⁱ—K1—O6ⁱⁱ	111.02 (10)	S1—O5—K1^vi	77.73 (11)
O5ⁱ—K1—O6ⁱⁱ	84.11 (8)	K1^v—O5—K1^vi	94.19 (7)
O3^iv—K1—O6	79.69 (8)	S1—O6—K1^vi	104.63 (13)
O7ⁱⁱⁱ—K1—O6	108.95 (10)	S1—O6—K1	119.49 (16)
O5ⁱ—K1—O6	161.50 (8)	K1^vi—O6—K1	109.29 (8)
O6ⁱⁱ—K1—O6	111.35 (7)	S1—O7—K1^vii	153.43 (16)
O3^iv—K1—S1ⁱⁱ	145.54 (6)	O4—C1—C6	120.2 (3)
O7ⁱⁱⁱ—K1—S1ⁱⁱ	101.41 (7)	O4—C1—C2	115.6 (3)
O5ⁱ—K1—S1ⁱⁱ	102.33 (6)	C6—C1—C2	124.2 (3)
O6ⁱⁱ—K1—S1ⁱⁱ	24.13 (6)	C1—C2—C3	116.1 (3)
O6—K1—S1ⁱⁱ	95.45 (5)	C1—C2—S1	120.0 (2)
O3^iv—K1—O5ⁱⁱ	134.72 (7)	C3—C2—S1	123.8 (3)
O7ⁱⁱⁱ—K1—O5ⁱⁱ	109.43 (8)	O1—C3—C4	115.7 (3)
O5ⁱ—K1—O5ⁱⁱ	126.38 (7)	O1—C3—C2	123.2 (3)
O6ⁱⁱ—K1—O5ⁱⁱ	43.85 (7)	C4—C3—C2	121.1 (3)
O6—K1—O5ⁱⁱ	71.21 (6)	C5—C4—C3	120.9 (3)
S1ⁱⁱ—K1—O5ⁱⁱ	24.25 (4)	C5—C4—H4	119.5
O3^iv—K1—K1^vi	111.17 (5)	C3—C4—H4	119.5
O7ⁱⁱⁱ—K1—K1^vi	109.12 (6)	O2—C5—C4	119.4 (3)
O5ⁱ—K1—K1^vi	162.75 (6)	O2—C5—C6	119.7 (3)
O6ⁱⁱ—K1—K1^vi	79.25 (6)	C4—C5—C6	120.9 (3)
O6—K1—K1^vi	35.35 (5)	C1—C6—C5	116.8 (3)
S1ⁱⁱ—K1—K1^vi	60.42 (2)	C1—C6—C7	120.2 (3)
O5ⁱⁱ—K1—K1^vi	36.40 (4)	C5—C6—C7	123.0 (3)
O3^iv—K1—K1ⁱⁱ	117.97 (5)	O3—C7—C8	122.4 (3)
O7ⁱⁱⁱ—K1—K1ⁱⁱ	90.78 (8)	O3—C7—C6	121.6 (3)
O5ⁱ—K1—K1ⁱⁱ	49.41 (6)	C8—C7—C6	116.0 (3)
O6ⁱⁱ—K1—K1ⁱⁱ	35.37 (6)	C9—C8—C7	121.4 (3)
O6—K1—K1ⁱⁱ	146.71 (6)	C9—C8—H8	119.3
S1ⁱⁱ—K1—K1ⁱⁱ	53.48 (2)	C7—C8—H8	119.3
O5ⁱⁱ—K1—K1ⁱⁱ	77.10 (4)	C8—C9—O4	121.6 (3)
K1^vi—K1—K1ⁱⁱ	113.47 (3)	C8—C9—C10	127.9 (3)
O3^iv—K1—K1^viii	160.42 (6)	O4—C9—C10	110.5 (3)
O7ⁱⁱⁱ—K1—K1^viii	49.44 (7)	C11—C10—C15	118.2 (3)
O5ⁱ—K1—K1^viii	96.34 (5)	C11—C10—C9	121.0 (3)
O6ⁱⁱ—K1—K1^viii	71.15 (7)	C15—C10—C9	120.8 (3)
O6—K1—K1^viii	98.28 (6)	C10—C11—C12	121.9 (4)
S1ⁱⁱ—K1—K1^viii	53.85 (2)	C10—C11—H11	119.1
O5ⁱⁱ—K1—K1^viii	60.52 (4)	C12—C11—H11	119.1
K1^vi—K1—K1^viii	74.040 (15)	C13—C12—C11	119.4 (4)
K1ⁱⁱ—K1—K1^viii	74.040 (15)	C13—C12—H12	120.3
O5—S1—O6	111.97 (16)	C11—C12—H12	120.3
O5—S1—O7	111.99 (17)	C12—C13—C14	120.7 (4)
O6—S1—O7	112.33 (19)	C12—C13—H13	119.6
O5—S1—C2	108.86 (15)	C14—C13—H13	119.6
O6—S1—C2	106.85 (15)	C13—C14—C15	119.5 (4)
O7—S1—C2	104.36 (16)	C13—C14—H14	120.3
O5—S1—K1^vi	78.02 (11)	C15—C14—H14	120.3
O6—S1—K1^vi	51.24 (10)	C14—C15—C10	120.3 (4)
O7—S1—K1^vi	92.71 (12)	C14—C15—H15	119.8
C2—S1—K1^vi	156.86 (12)	C10—C15—H15	119.8
C3—O1—H1	109.5

O6—S1—O5—K1^v	−89.8 (8)	O5—S1—C2—C3	−127.7 (3)
O7—S1—O5—K1^v	37.4 (8)	O6—S1—C2—C3	111.2 (3)
C2—S1—O5—K1^v	152.3 (7)	O7—S1—C2—C3	−8.0 (3)
K1^vi—S1—O5—K1^v	−50.7 (7)	K1^vi—S1—C2—C3	128.4 (3)
O6—S1—O5—K1^vi	−39.14 (14)	C1—C2—C3—O1	179.6 (3)
O7—S1—O5—K1^vi	88.08 (15)	S1—C2—C3—O1	2.9 (5)
C2—S1—O5—K1^vi	−157.05 (13)	C1—C2—C3—C4	0.4 (5)
O5—S1—O6—K1^vi	52.35 (18)	S1—C2—C3—C4	−176.3 (3)
O7—S1—O6—K1^vi	−74.68 (17)	O1—C3—C4—C5	−179.4 (3)
C2—S1—O6—K1^vi	171.45 (13)	C2—C3—C4—C5	−0.1 (5)
O5—S1—O6—K1	175.02 (14)	C3—C4—C5—O2	178.0 (3)
O7—S1—O6—K1	48.0 (2)	C3—C4—C5—C6	−0.8 (5)
C2—S1—O6—K1	−65.88 (19)	O4—C1—C6—C5	177.3 (3)
K1^vi—S1—O6—K1	122.7 (2)	C2—C1—C6—C5	−1.0 (4)
O3^iv—K1—O6—S1	86.63 (17)	O4—C1—C6—C7	−1.9 (4)
O7ⁱⁱⁱ—K1—O6—S1	−23.78 (19)	C2—C1—C6—C7	179.7 (3)
O5ⁱ—K1—O6—S1	68.3 (4)	O2—C5—C6—C1	−177.4 (3)
O6ⁱⁱ—K1—O6—S1	−146.56 (11)	C4—C5—C6—C1	1.3 (5)
S1ⁱⁱ—K1—O6—S1	−127.83 (16)	O2—C5—C6—C7	1.8 (5)
O5ⁱⁱ—K1—O6—S1	−128.54 (18)	C4—C5—C6—C7	−179.5 (3)
K1^vi—K1—O6—S1	−120.4 (2)	K1^iv—O3—C7—C8	−19.5 (6)
K1ⁱⁱ—K1—O6—S1	−147.10 (9)	K1^iv—O3—C7—C6	161.6 (3)
K1^viii—K1—O6—S1	−73.63 (16)	C1—C6—C7—O3	179.0 (3)
O3^iv—K1—O6—K1^vi	−153.01 (12)	C5—C6—C7—O3	−0.2 (5)
O7ⁱⁱⁱ—K1—O6—K1^vi	96.58 (12)	C1—C6—C7—C8	0.0 (4)
O5ⁱ—K1—O6—K1^vi	−171.4 (2)	C5—C6—C7—C8	−179.2 (3)
O6ⁱⁱ—K1—O6—K1^vi	−26.21 (19)	O3—C7—C8—C9	−177.0 (3)
S1ⁱⁱ—K1—O6—K1^vi	−7.48 (11)	C6—C7—C8—C9	1.9 (5)
O5ⁱⁱ—K1—O6—K1^vi	−8.18 (9)	C7—C8—C9—O4	−2.0 (5)
K1ⁱⁱ—K1—O6—K1^vi	−26.7 (2)	C7—C8—C9—C10	179.1 (3)
K1^viii—K1—O6—K1^vi	46.72 (11)	C1—O4—C9—C8	0.1 (4)
O5—S1—O7—K1^vii	−24.2 (5)	C1—O4—C9—C10	179.1 (2)
O6—S1—O7—K1^vii	102.8 (5)	C8—C9—C10—C11	−8.7 (5)
C2—S1—O7—K1^vii	−141.8 (4)	O4—C9—C10—C11	172.3 (3)
K1^vi—S1—O7—K1^vii	54.0 (5)	C8—C9—C10—C15	171.8 (3)
C9—O4—C1—C6	1.9 (4)	O4—C9—C10—C15	−7.2 (4)
C9—O4—C1—C2	−179.6 (2)	C15—C10—C11—C12	−1.1 (6)
O4—C1—C2—C3	−178.2 (3)	C9—C10—C11—C12	179.5 (4)
C6—C1—C2—C3	0.2 (5)	C10—C11—C12—C13	−0.5 (8)
O4—C1—C2—S1	−1.4 (4)	C11—C12—C13—C14	1.6 (8)
C6—C1—C2—S1	177.0 (2)	C12—C13—C14—C15	−1.0 (7)
O5—S1—C2—C1	55.8 (3)	C13—C14—C15—C10	−0.6 (6)
O6—S1—C2—C1	−65.3 (3)	C11—C10—C15—C14	1.7 (5)
O7—S1—C2—C1	175.5 (3)	C9—C10—C15—C14	−178.9 (3)
K1^vi—S1—C2—C1	−48.2 (4)

Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1/2, y, z+1/2; (iv) −x, −y+1, −z+1; (v) x, y, z−1; (vi) x, −y+1/2, z−1/2; (vii) −x+1/2, y, z−1/2; (viii) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7	0.82	1.84	2.588 (4)	152
O2—H2···O3	0.82	1.87	2.604 (4)	148

Experimental details

Crystal data
Chemical formula	[K(C₁₅H₉O₇S)]
M_r	372.38
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	296
a, b, c (Å)	19.0846 (19), 20.6555 (19), 7.5148 (7)
V (Å³)	2962.3 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.54
Crystal size (mm)	0.37 × 0.20 × 0.13

Data collection
Diffractometer	Bruker SMART1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.825, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	13998, 2637, 1746
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.152, 1.02
No. of reflections	2637
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.29

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

K1—O5ⁱ	2.674 (2)	K1—O3^iv	2.642 (2)
K1—O6ⁱⁱ	2.754 (2)	K1—O6	2.756 (3)
K1—O7ⁱⁱⁱ	2.655 (3)

Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1/2, y, z+1/2; (iv) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7	0.82	1.84	2.588 (4)	152
O2—H2···O3	0.82	1.87	2.604 (4)	148

Acknowledgements

Financial support for this work from the Natural Science Foundation of Shaanxi Province (2005B01), the National Basic Research Program of China (973 Program, 2009CB219906), the National Natural Science Foundation of China (20776117) and the Specialized Research Fund for the Doctoralal Program of Higher Education of China (20070698037) are gratefully acknowledged.

References

Aljancic, I., Vajs, V., Menkovic, N., Karadzic, I., Juranic, N., Milosavljevic, S. & Macura, S. (1999). J. Nat. Prod. 62, 909–911. Web of Science PubMed CAS Google Scholar
Benedict, J. B., Bullard, T., Kaminsky, W. & Kahr, B. (2004). Acta Cryst. C60, m551–m553. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bruker (1999). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Habtemariam, S. (1997). J. Nat. Prod. 60, 775–778. CrossRef CAS PubMed Web of Science Google Scholar
Knekt, P., Jarvinen, R., Seppanen, R., Heliovaara, M., Pukkala, L. T. & Aromaa, A. (1997). Am. J. Epidemiol. 146, 223–230. CrossRef CAS PubMed Web of Science Google Scholar
Ko, F., Chu, C., Lin, C., Chang, C. & Teng, C. (1998). Biochim. Biophys. Acta, 1389, 81–90. Web of Science CrossRef CAS PubMed Google Scholar
Li, W.-W. & Zhang, Z.-T. (2008). Acta Cryst. C64, m176–m178. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nkengfack, A., Vouffo, T., Fomun, Z., Meyer, M. & Bergendorff, S. O. (1994). Phytochemistry, 36, 1047–1051. CrossRef CAS PubMed Web of Science Google Scholar
Sakaguchi, Y., Maehara, Y., Baba, H., Kusumoto, T., Sugimachi, K. & Newmanv, R. A. (1992). Cancer Res. 52, 3306–3309. PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Q.-Y. & Zhang, Z.-T. (2005a). Acta Cryst. C61, m215–m217. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Wang, X. B. & Zhang, Z. T. (2005b). Z. Kristallogr. New Cryst. Struct. 220, 223–225. CAS Google Scholar
Zhang, Z. T. & Wang, Q. Y. (2005a). Heterocycles, 65, 1947–1956. CrossRef CAS Google Scholar
Zhang, Z. T. & Wang, Q. Y. (2005b). Struct. Chem. 16, 415–420. Web of Science CSD CrossRef CAS Google Scholar