Preparation and crystal structure of genistein benzenesulfonate prodrugs

Article abstract of DOI:10.3184/030823408X356297

In order to improve bioavailability and anticancer activity of genistein, a series of novel sulfonic acid ester prodrugs of the isoflavone genistein were synthesised in high yield with excellent regioselectivity. Their structures were characterised by IR, MS, elemental analysis and ¹H NMR spectra. The crystal structure was examined by X-ray diffraction. X-ray structure determination revealed that all the aromatic rings in the compound are not coplanar. In the crystal structure, molecules are linked through intermolecular C-H...O hydrogen bonds, forming layers parallel to the ab plane.

Full text of DOI:10.3184/030823408X356297

JOURNAL OF CHEMICAL RESEARCH 2008
OCTOBER, 555–558
RESEARCH PAPER 555
Preparation and crystal structure of genistein benzenesulfonate prodrugs
You Penga,b Zeyuan Denga* Shaojie Langb and Yawei Fana
aState Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047, P.R. China
bDepartment of Chemistry and Engineering, Jiujiang University, Jiujiang 332005, P.R. China
In order to improve bioavailability and anticancer activity of genistein, a series of novel sulfonic acid ester prodrugs
of the isoflavone genistein were synthesised in high yield with excellent regioselectivity. Their structures were
characterised by IR, MS, elemental analysis and 1H NMR spectra. The crystal structure was examined by X-ray
diffraction. X-ray structure determination revealed that all the aromatic rings in the compound are not coplanar. In
the crystal structure, molecules are linked through intermolecular C–H∙∙∙O hydrogen bonds, forming layers parallel
to the ab plane.
Keywords: synthesis, pro-drug, sulfonic acid ester, crystal structure, hydrogen bonding
Genistein, a natural kudzuvine root isoflavone, possesses
many biological activities such as phytoestrogen,1
antidysrhythmic2 and antioxidant.3,4 Especially, it is arousing
infinite interests in the world because it can restrain manifold
cancer cells.5 Unfortunately, its poor lipophilicity and first
pass effect will result to weak bioavailability due to three
polar hydroxyls.6 Accordingly, we have developed a program
to prepare isoflavone analogues.7 The title compounds, 3–9
are prodrugs of genistein with potential anticancer activities.
In order to further improve the bioavailability and biological
Fig. 1 Molecular structure of 9. Displacement ellipsoids are
plotted at the 30% probability level.
activity of the genistein and study metabolic mechanism of
its derivatives, we now present the first chemical synthesis of
its sulfonic acid esters and crystal structure of its analogue 9.
X-ray structure determination revealed that all the aromatic
rings in the compound are not coplanar with each other.
In the crystal structure 9 (a = 14.802(3) Å, b = 6.088(2) Å,
c = 28.648(6) Å, a = b = g = 90o, V = 2581.6(9) Å3, Z = 4, space
group Pca21), molecules are linked through intermolecular
C–H∙∙∙O hydrogen bonds, forming layers parallel to the ab
plane.
Yellow block crystals suitable for single crystal X-ray
diffraction were obtained by slow evaporation of the solvent
from CH2Cl2 solution.Asingle crystal selected for investigation
had dimensions of 0.28 mm × 0.27 mm × 0.27 mm. Figure 1
gives a perspective view of the molecular structure of
compound 9 with the atomic labelling system. Selected bond
lengths and angles are summarised in Table 1. The compound
is composed of three aromatic rings and a chromen ring,
C1–C6 (A), C7–C15/O6 (B), C17–C22 (C), C23–C28 (D), a
methoxy moiety, and two bridging SO3 moieties. All the bond
lengths and angles in the compound are within normal ranges.8
To avoid steric conflicts, the rings B and C are not coplanar,
with the dihedral angle of 51.6(2)o. The C16 atom deviates
from the parent ring B by 0.486(2) Å. As expected, each
S atom is located at the centre of the tetrahedral geometry.
The bond angles subtended at the S1 and S2 atoms are ranged
from 102.1(2)–121.0(2)o and 100.0(2)–118.0(2)o, respectively,
Fig. 2 Molecular packing of 9, viewed along the b axis.
Hydrogen bonds are shown as dashed lines.
indicating that the tetrahedral geometries are deviated from the
ideal tetrahedral configurations. The dihedral angle between
the rings A and B is 43.6(3)o, and that between rings C and
D is 11.6(3)o. The torsion angles C1–S1–O3–C7 and C20–
O7–S2–C23 are 65.9(2)o and 11.2(2)o, respectively. In the
crystal structure, molecules are linked through intermolecular
C–H∙∙∙O hydrogen bonds, forming layers parallel to the ab
plane (Fig.2). Hydrogen bonds are listed in Table 2.
The possible main reason of the poor bioavailability of
genistein is its first pass effect in vivo. Consequently, in this
experiment in order to enhance bioavailability of genistein,
its 7-hydroxyl was esterified for stopping the first pass effect
according to the prodrug barnbuterol of terbutaline design
idea.10
In addition, relatively shorter centroid distances (Table 3)
among the rings are observed, implying the existence of π–π
stacking interactions in the compound.
Despite the acidity of 7-OH in the genistein exhibits a
hundred-fold compared to the 4'-hydroxy group and 5-OH
is stabilised by hydrogen-bond,10 we tried to use different
equivalent of acyl chloride by using pyridine as base and
CH2Cl2 as solvent at low temperature, the major product
* Correspondent. Email: dengzeyuanpaper@126.com

556 JOURNAL OF CHEMICAL RESEARCH 2008
Table 1 Selected bond distances (Å) and angles (o) for 3
ethylation of all hydroxyl. The results showed that the effect
of hydrogen-bond stabilisation exceeds activity of alkylation
rection of 5-hydroxy group in genistein. Also we cannot
obtain the ethylation product of 5. If we improve the reaction
temperature for the reaction of 5 and diethylsulfate, byproduct
4',5,7-triethylgenistein formed alike.
The title compounds were synthesised with high yield and
high regioselectivity as shown in Scheme 1. The studies on
the solubility and lipid/water partition coefficient logP of the
title compounds are in progress.
Bond distances
S1–O2
S1–O3
S2–O8
S2–O7
O3–C7
O4–C16
O6–C13
O7–C20
1.421(3)
1.594(3)
1.421(3)
1.589(2)
1.432(4)
1.418(4)
1.356(4)
1.439(4)
S1–O1
1.422(3)
1.762(5)
1.423(3)
1.736(4)
1.362(4)
1.228(4)
1.373(4)
1.477(5)
S1–C1
S2–O9
S2–C23
O4–C9
O5–C11
O6–C14
C12–C17
Bond angles
Experimental
1H NMR spectra was recorded in CDCl3 on Varian INOVA 400 MHz
spectrometer, using TMS as internal standard. FT-IR spectra were
recorded on a Nicocet 5700 FT-IR spectrophotometer. MS spectra
were recorded on a Waters ZQ4000/2695 micromass. Melting points
were determined with a WARR Melting Point Apparatus and are
uncorrected. The crystal structure was determined using a Bruker
SMART CCD area-detector diffractometer. Elemental analysis was
performed by Central Service of Nanchang University, People's
Republic of China, and the result was found to be within ±0.3% of
predicted values for compounds 3–9.
O2–S1–O1
O1–S1–O3
O1–S1–C1
O8–S2–O9
O9–S2–O7
O9–S2–C23
C7–O3–S1
C13–O6–C14
C2–C1–S1
C15–C7–O3
O4–C9–C8
O5–C11–C10
C13–C12–C17
C22–C17–C12
C19–C20–O7
C28–C23–S2
121.0(2)
102.9(2)
110.5(2)
118.0(2)
108.8(2)
109.2(2)
117.5(2)
117.4(3)
119.6(4)
118.7(3)
122.9(4)
124.2(4)
120.4(3)
121.0(3)
119.5(3)
119.8(3)
O2–S1–O3
O2–S1–C1
109.9(2)
108.7(2)
102.1(2)
109.2(2)
110.2(2)
100.0(2)
119.4(3)
115.0(2)
118.2(4)
116.8(3)
116.3(3)
120.8(3)
121.3(3)
120.1(3)
118.0(3)
119.0(3)
O3–S1–C1
O8–S2–O7
O8–S2–C23
O7–S2–C23
C9–O4–C16
C20–O7–S2
C6–C1–S1
C8–C7–O3
O4–C9–C10
O5–C11–C12
C11–C12–C17
C18–C17–C12
C21–C20–O7
C24–C23–S2
Synthetic procedure
Preparation of 3-(4-benzenesulfonylphenyl)-5,7-bis(benzenelsulfonyl)-
4H-chromen-4-one (3): A solution of genistein 0.270 g (1 mmol) and
benzenesulfonic acid chloride 0.58 ml(4.5 mmol) in 5 ml pyridine was
stirred at –20°C for 3 h under Ar. Pouring it into ice water followed
by extraction with ether/ethyl acetate (1/2), washing with aqueous
NaHCO3, drying and removal of solvent under reduced pressure
gives the crude product. Purification by flash chromatography (silica,
CH2Cl2) yields white solid 3(0.683 g, 99% yield); m.p. 150–152°C;
IR (KBr): 3092, 1659; 1H NMR(CDCl3) δ: 7.98–7.90(m, 6H, 2", 2''',
2"'', 6", 6''',6"'' –benH), 7.82(s, 1H, 2-H), 7.77–7.72(m, 3H, 4'', 4''',
4''''-H), 7.58(m, 6H, 3", 3''', 3'''',5",5''',5''''-benH), 7.39 (d, 2H, 2',6'-
ArH, J = 8.5 Hz), 7.22(d, 1H, 8-ArH, J = 1.88 Hz), 7.05(d, 2H, 3',5'-
ArH, J = 8.5 Hz), 6.81(d, 1H, 6-ArH, J = 1.5 Hz); m/z (EI) 691.18
(M+ + 1, 100%). Anal. Calcd for C33H22O11S3: C 57.38, H 3.21,
S 13.93; found C 57.30, H 3.22, S 13.91.
Table 2 Geometrical parameters for hydrogen bonds for 3
Hydrogen bonds
D–H (Å) H∙∙∙A (Å) D∙∙∙A (Å) D–H∙∙∙A (o)
C2–H2∙∙∙O2
0.93
0.93
0.93
0.93
0.93
0.93
2.55
2.31
2.53
2.58
2.54
2.54
2.917(3)
3.212(3)
3.404(3)
2.942(3)
3.435(3)
2.900(3)
104
163
156
104
163
104
C18–H18∙∙∙O5#1
C19–H19∙∙∙O6#2
C22–H22∙∙∙O5
C27–H27∙∙∙O8#2
C28–H28∙∙∙O9
Preparationof3-(4-hydroxylphenyl)-5-hydroxy-7-benzenelsulfonyl-
4H-chromen-4-one (4): A solution of genistein 0.270 g (1 mmol) and
1 ml pyridine in dry THF (4 ml) was stirred at –20°C for 0.5 h under
Ar, the benzenesulfonic acid chloride 0.2 ml (1.5 mmol) in THF (3 ml)
was added to this solution over 15 minutes and the reaction continued
for 5 min. Pouring it into ice water followed by extraction with
ether/ethyl acetate (1/2), washing with aqueous NaHCO3, drying and
removal of solvent under reduced pressure gives the crude product.
Purification by flash chromatography (silica, CHCl3/(CH3)2CO, 10/1)
yields white solid 4(0.369 g, 90% yield). m.p. 154–156°C; IR (KBr):
3081, 1616; 1H NMR(CDCl3) δ:12.7(s, 1H, 5-OH), 7.94(s, 1H, 2-H),
7.90(d, 2H, 2",6"-benH, J = 7.7 Hz), 7.72(t, 1H, 4''-H, J = 7.5 Hz),
7.59(t, 2H, 3",5"-benH, J = 7.7 Hz), 7.39 (d, 2H, 2',6'-ArH, J = 8.5 Hz),
6.90(d, 2H, 3',5'-ArH, J = 8.5 Hz), 6.77(d, 1H, 8-ArH J = 2.0 Hz),
6.39(d, 1H, 6-ArH, J = 2.0 Hz), 5.39(s, 1H, 4'-OH); m/z (EI) 411.08
(M+ + 1, 100%). Anal. Calcd for C21H14O7S: C 61.46, H 3.44, S 7.81;
found C 61.37, H 3.44, S 7.79.
#1 x, 1 + y, z, #2 –1/2 + x, 2 – y, z
isoflavone 4',5,7-triesters 3 formed. When we controlled the
reaction condition using different equivalent of acyl chloride
of benzenesulfonyl chloride in THF solvent system, the
compounds 4 and 5 formed in high yields respectively. Possibly,
the solvent effect resulted to the good regioselectivity.
The title compound 6 was synthesised by ethylation from
the compound 4. We use excess diethyl sulfate (10 fold
equiv.), the title compound 6 is the only product and 4',5-
diethyl-7-phenylsulfonylgenistein cannot be obtained.
The hydrogen-bond stabilised 5-hydroxy group in genistein
might not react at 0°C. When we improved the reaction
temperature, the compound 4 undergo desulfonate and
Table 3 Parameters between the planes for 9
Cg
Distance between
ring centroids/Å
Dihedral
angle/o
Perpendicular
distance of Cg(I) on
Cg(J)/Å
Perpendicular
distance of Cg(J) on
Cg(I)/Å
Cg(1) Æ Cg(3)[1545]
Cg(1) Æ Cg(3)[4565]
Cg(1) Æ Cg(4)[4465]
Cg(1) Æ Cg(5)[4465]
Cg(2) Æ Cg(3)[1555]
Cg(1) Æ Cg(5)[3554]
Cg(3) Æ Cg(4)[4465]
Cg(4) Æ Cg(5)[4455]
Cg(4) Æ Cg(5)[4465]
Cg(5) Æ Cg(2)[3545]
5.501
5.954
4.203
5.799
4.577
4.728
3.749
5.205
4.523
5.049
3.46
58.70
6.31
11.07
44.16
50.53
8.60
45.30
45.30
50.53
3.063
3.250
3.466
4.826
2.767
2.428
3.592
2.073
4.308
1.817
2.942
3.307
3.364
4.272
3.560
4.675
3.395
4.840
2.550
4.663
Cg(1): C(1) Æ C(2) Æ C(3) Æ C(4) Æ C(5) Æ C(6) Æ
Cg(2): C(7) Æ C(8) Æ C(9) Æ C(10) Æ C(14) Æ C(15) Æ
Cg(3): C(17) Æ C(18) Æ C(19) Æ C(20) Æ C(21) Æ C(22) Æ
Cg(4): C(23) Æ C(24) Æ C(25) Æ C(26) Æ C(27) Æ C(28) Æ
Cg(5): O(6) Æ C(13) Æ C(12) Æ C(11) Æ C(10) Æ C(9) Æ C(8) Æ C(7) Æ C(15) Æ C(14) Æ

JOURNAL OF CHEMICAL RESEARCH 2008 557
R3O
O
SO2Cl
HO
O
O
a
OR1
+
OH
OR2
O
OH
1
3 R1=R2=R3=phenylsulfonyl
2
4
R1=R2=H, R3=phenylsulfonyl
5 R2=H, R1=R3=phenylsulfonyl
O
O
O
S
OR1
O
O
b
4
7
6
OR2
c
6 R1=CH2CH3, R2=H
7 R1=R2=COCH3
O
O
O
O
O
S
S
O
O
O
8
OR
c
8 R=COCH3
9 R=CH3
9
5
d
a: pyridine, dry THF, Ar, –20 °C b: KOH, diethylsulfate, acetone, 0 °C
c: acetic anhydride, dry pyrid d: K CO , dry acetone, dimethylsulf
°C
0 °C
2
3
Scheme 1 Structures of isoflavone genistein sulfonic acid esters
Preparation of 3-(4-benzenesulfonylphenyl)-7-benzenelsulfonyl-
5-hydroxy-4H-chromen-4-one (5): A solution of genistein 0.270 g
(1 mmol) and 0.1 g potassium tert-butoxide in dry THF (2 ml) was stirred
at –20°C for 0.5 h under Ar, the benzenesulfonic acid chloride 0.4 ml
(2.6 mmol) in THF (3 ml) was instilled to this solution in 15 minutes
and the reaction continued for 3 h. Pouring it into ice water followed
by extraction with ether/ethyl acetate (1/2), washing with aqueous
NaHCO3, drying and removal of solvent under reduced pressure
gives the crude product. Purification by flash chromatography
(silica, CH2Cl2/PE, 4/1) yields white solid 5 (0.446 g, 81% yield).
m.p. 158–159°C. IR (KBr): 3081, 1642; 1H NMR(CDCl3) δ: 12.7(s,
1H, 2-OH), 7.95(s, 1H, 2-H), 7.90(d, 4H, 2",6"-benH, 2''',6'''-benH,
J = 8.7,9.3 Hz), 7.72(m, 2H, 4'', 4'''-H), 7.58(m, 4H, 3", 3''', 5",5'''
-benH),7.46 (d, 2H, 2',6'-ArH, J = 8.5 Hz), 7.09(d, 2H, 3',5'-ArH,
J = 8.5 Hz), 6.77(d, 1H, 8-ArH, J = 1.5 Hz), 6.39(d, 1H, 6-ArH,
J = 1.5 Hz); m/z (EI) 550.96 (M+ + 1, 90%).Anal. Calcd for C27H18O9S2:
C 58.90, H 3.30, S 11.65; found C 58.80, H 3.31, S 11.63.
Preparation of 3-(4-ethoxyphenyl)-5-hydroxy-7-benzenelsulfonyl-
4H-chromen-4-one (6):Asolution of 2(0.123 g,0.3 mmol) and 0.0957 g
KOH in 20 ml acetone was stirred at 0°C for 30 min, the diethylsulfate
0.4 ml(3.0 mmol) in acetone (5 ml) was instilled to this solution in
15 min and the reaction continued for 24 h. Pouring it into ice water
followed by extraction with ethyl acetate, washing with aqueous
NaHCO3, drying and removal of solvent under reduced pressure gives
the crude product. The crude product was recrystallised in MeOH to
produce a white crystal 6(0.118 g, 90%yield). m.p. 110–111°C; IR
(KBr): 3069,1650; 1H NMR(CDCl3) δ: 12.9(s, 1H, 5-OH), 7.94(s, 1H,
2-H), 7.92(d, 2H, 2",6"-benH, J = 7.8 Hz), 7.72(t, 1H, 4''-H, J = 7.4 Hz),
7.59(t, 2H, 3",5"-benH, J = 7.7 Hz),7.39 (d, 2H, 2',6'-ArH, J = 8.4 Hz),
6.90(d, 2H, 3',5'-ArH, J = 8.4 Hz), 6.77(s, 1H, 8-ArH), 6.39(s, 1H, 6-
ArH),4.08(dd,2H,4'-OCH2-,J=6.9Hz),1.45(t,1H,4'-CH3,J=6.9Hz);
m/z (EI) 439.26 (M+ + 1, 100%). Anal. Calcd for C23H18O7S: C 63.01,
H 4.14, S 7.31; found C 62.85, H 4.15, S 7.29.
7.11(d, 1H, 8-ArH, J = 2.0 Hz), 6.68(d, 1H, 6-ArH, J = 2.0 Hz),
2.38(s, 3H, 5-OCCH3), 2.31(s, 3H, 4'-OCCH3); m/z (EI) 495.38 (M+
+ 1, 100%). Anal. Calcd for C25H18O9S: C 60.73, H 3.67, S 6.45;
found C 60.61, H 3.68, S 6.44.
Preparation of 3-(4-benzenelsulfonylphenyl)-7-benzenelsulfonyl-
5-acetyl-4H-chromen-4-one (8): A solution of 3(0.205 g,0.5 mmol)
and 0.11 ml acetic anhydride in 20 ml dry pyridine was stirred
at 0°C for 24 h. Pouring it into ice water followed by extraction
with ethyl acetate, washing with aqueous NaHCO3, drying and
removal of solvent under reduced pressure gives the crude product.
ThecrudeproductwasrecrystallisedinEtOHtoproduceawhitesolid8
(0.290g,98%yield).m.p.187–188°C;IR(KBr):3100,1767,1646cm-1;
Table 4 Crystal data and refinement parameters for 9
CCDC deposit no.
Molecular formula
Molecular weight
Temperature (K)
Radiation l
676225
C28H20O9S2
564.56
298(2)
Mo K a(0.71073 Å)
Orthorhombic
Pca21
Crystal system
Space group
a/Å
14.802(3)
6.088(2)
b/Å
c/Å
28.648(6)
2581.6(9)
4
V/Å 3
Z
Dcalc (g cm-3)
1.453
Crystal size (mm)
Crystal colour
0.28 × 0.27 × 0.27
Colourless
0.262
0.930 and 0.933
1168
Absorption coefficient (cm-1)
Absorption correction Tmin and Tmax
F(000)
Reflections collected/unique
Range/indices (h, k, l)
q limit (o)
No. of observed data, I > 2s(I)
No. of variables
No. of restraints
Goodness of fit on F2
R1, wR2 [I ≥ 2s(I)]a
R1, wR2 (all data)a
16270/5301 [Rint = 0.0682]
–18, 18; –7, 7; –35, 35
2.75–26.50
2485
Preparation of 3-(4-acetoxyphenyl)-5-acetyl-7-benzenelsulfonyl-
4H-chromen-4-one (7): A solution of 2(0.205 g,0.5 mmol) and 0.23 ml
acetic anhydride in 20 ml dry pyridine was stirred at 0°C for 24 h.
Pouring it into ice water followed by extraction with ethyl acetate,
washing with aqueous NaHCO3, drying and removal of solvent
under reduced pressure gives the crude product. The crude product
was recrystallised in EtOH to produce a white crystal 7(0.242 g,
354
1
0.839
0.0403, 0.0808
0.1113, 0.0940
1
98%yield). m.p. 169–170°C; IR (KBr):3087, 1747, 1649; H NMR
(CDCl3) δ:7.90(d, 2H, 2",6"-benH, J = 8.0 Hz), 7.88(s, 1H, 2-H),
7.73(t, 1H, 4''-H, J = 7.5 Hz), 7.59(t, 2H, 3",5"-benH, J = 7.7 Hz),
7.47 (d, 2H, 2',6'-ArH, J = 8.5 Hz), 7.15(d, 2H, 3',5'-ArH, J = 8.5 Hz),
aR1 = S||Fo|-|Fc||/S|Fo|, wR2 = [Sw(Fo2-Fc2)2/Sw(Fo2)2]1/2, w= [s2(Fo) 2
+ (0.0417(Fo2 + 2Fc2)/3)2]-1.

558 JOURNAL OF CHEMICAL RESEARCH 2008
1H NMR(CDCl3) δ: 7.90(dd, 4H, 2",2''',6",6'''-benH, J = 2.5,
8.0 Hz), 7.86(s, 1H, 2-H), 7.73(m, 2H, 4''',4''-H), 7.59(m, 4H,
3",3''',5",5'''-benH),7.40 (d, 2H, 2',6'-ArH, J = 8.4 Hz), 7.17(d, 1H,
8-ArH, J = 2.0 Hz),7.05(d, 2H, J = 8.4 Hz, 3',5'-ArH, J = 8.4 Hz),
6.68(d, 1H, 6-ArH, J = 2.0 Hz), 2.37(s, 3H, 5-OCCH3); m/z (EI)
593.23 (M+ + 1, 100%). Anal. Calcd for C29H20O10S2: C 58.78,
H 3.40, S 10.82; found C 58.65, H 3.40, S 10.79.
Preparation of 3-(4-benzenesulfonylphenyl)-7-benzenesulfonyl-5-
methoxy-4H-chromen-4-one (9): A solution of 5(0.165 g, 0.3 mmol)
and 0.601 g K2CO3 in 30 ml dry acetone was stirred at 0°C for
30 min, the dimethylsulfate 0.36 ml(3.8 mmol) in dry acetone (5 ml)
was instilled to this solution in 15 min and the reaction continued
for 24 h. Filtering and removal of acetone under reduced pressure
gives the crude product. The crude product was recrystallised
in EtOH to produce a white crystal 9 (0.157 g, 95%yield). m.p.
80–81°C; IR (KBr):1767, 1645; 1H NMR(CDCl3) δ: 7.90(dd, 4H,
2",2''',6",6'''-benH, J = 2.5,8.0 Hz), 7.80(s,1H, 2-H-), 7.75 (m, 2H,
4''',4''-H), 7.58(m, 4H, 3",3''',5",5'''-benH), 7.45 (d, 2H, 2',6'-ArH,
J = 8.4 Hz), 7.02(d, 2H, 3',5'-ArH, J = 8.4 Hz), 6.76(s, 1H, 8-ArH,
J = 2.0 Hz),6.42(s, 1H, 6-ArH, J = 2.0 Hz), 3.82(s, 3H, CH3); MS,
m/z: 565.26 (M+ + 1). Anal. Calcd for C28H20O9S2: C 59.57, H 3.57,
S 11.36. Found: C 59.43, H 3.57, S 11.33.
The authors acknowledge support from the Opening
Foundation of the State Key Laboratory of Food Science
and Technology in Nanchang University (No. NCU200508),
the Program for Changjiang Scholars and Innovative
Research Team of the Ministry of Education of China
(No. IRTO540) and the Science and Technology Item of the
Education Department of Jiangxi Province (No. GJJ08440).
Received 10 June 2008; accepted 11 August 2008
Paper 08/5320 doi: 10.3184/030823408X356297
Published online: 3 October 2008
References
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X-ray diffraction analysis
The data were collected on a Bruker SMART CCD area-detector
diffractometer using graphite-monochromated Mo Ka radiation
(l = 0.71073 Å) by ω scan mode within the angular range 2.75°
< q < 26.50°. The collected data were reduced using the SAINT
program,11 and empirical absorption corrections were performed
using the SADABS program.12 The structure was solved by direct
methods and refined against F2 by full-matrix least-squares methods
using the SHELXTL program.13 All of the non-hydrogen atoms were
refined anisotropically. All hydrogen atoms were set in idealised
positions and refined using the riding model. The details of the
crystallographic data are summarised in Table 4. Crystallographic
data for 9 have been deposited with the Cambridge Crystallographic
Data Centre (CCDC No. 676225). Copies of available materials can
be obtained free of charge on application to the Director, CCDC,
12 Union Road, Cambridge CB2 IEZ, UK (fax: (44)01223 336033);
e-mail: deposit@ccdc.ac.uk).
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