Synthesis and single crystal X-ray structure of [Na(H2O) 2(C18H15O6SO3)] 2

Article abstract of DOI:10.1007/s10870-008-9406-y

[Na(H₂O)₂(C₁₈H₁₅O ₆SO₃)]₂ was synthesized by sulfated 5-hydroxy-6,7,4′-trimethoxyisoflavone with concentrated sulfuric acid. Single-crystal X-ray diffraction study indicates that

Full text of DOI:10.1007/s10870-008-9406-y

J Chem Crystallogr (2008) 38:861–865
DOI 10.1007/s10870-008-9406-y
ORIGINAL PAPER
Synthesis and Single Crystal X-Ray Structure
of [Na(H2O)2(C18H15O6SO3)]2
Xue-Ling Zhang Æ Zun-Ting Zhang Æ
Yong Liang
Received: 5 April 2006 / Accepted: 7 May 2008 / Published online: 23 May 2008
Ó Springer Science+Business Media, LLC 2008
Abstract [Na(H2O)2(C18H15O6SO3)]2 was synthesized
by sulfated 5-hydroxy-6,7,40-trimethoxyisoflavone with
concentrated sulfuric acid. Single-crystal X-ray diffraction
study indicates that it is a dimeric centrosymmetric species.
The coordination polyhedron of each Na(I) atom exhibits a
distorted trigonal bipyramidal geometry. The dimeric units
are linked by intermolecular hydrogen bonds C–H_p,
C–H_O and O–H_O to result in a three-dimensional
framework.
sulfates [2–6], especially the biological activities of sodium
7,40-dihydroxyisoflavone-30-sulfonate [7] and sodium 40-
hydroxy-7-methoxyisoflavone-30-sulfonate [8]. The results
showed that the biological activities of flavonoid sulfates
were better compared with the parent flavonoids. Irisoli-
done (5,7-dihydroxy-6,40-dimethoxyisoflavone) had the
most potent inhibitory activity against Helicobacter pylori
(HP) [9] and reduced the ethanol-induced mortality as well
as serum alanine aminotransferase (ALT) and aspartate
aminotransferase (AST) activities [10–12]. Furthermore,
these activities were dramatically affected by the position
of alkyls of the isoflavone skeleton [13]. In this paper,
irisolidone as leading compound, a water soluble flavonoid
sulfate ([Na(H2O)2(C18H15O6SO3)]2) was synthesized (the
route of synthesis in Scheme 1) and its structure was elu-
cidated by single-crystal X-ray diffraction (XRD), element
Keywords [Na(H2O)2(C18H15O6SO3)]2 ꢀ
Crystal structure ꢀ C–H_p ꢀ Hydrogen bonds
Introduction
1
Flavonoid sulfate occupies an important position in the
field of natural products chemistry since they provide a
structural link between organic and inorganic components
in nature [1]. In our previous work, we have synthesized
and studied the crystal structures and of some flavonoid
analysis, IR and H NMR spectroscopy.
Experimental
Irisolidone (purity [ 98.0%) was isolated from the flowers
of Pueraia lobata (the flowers of Pueraia lobata were
collected from the Taibai Mountains of Shaan’xi province)
and identified by IR and 1H NMR. The chemicals and
solvents used in this work were of analytical grade avail-
able commercially and without further purification. The
infrared spectrum was recorded on a Nicollet 170SX FT-IR
spectrophotometer with KBr pellets in the 4000–500 cm-1
region. The melting point was determined using X4 melt-
ing point instrument (The thermometer had not been
emended). The 1H NMR spectrum was recorded on a
Bruker AM-300 spectrometer with TMS as internal refer-
ence and DMSO-d6 as solvent. C and H contents were
analyzed using a PE-2400 elemental analytic instrument.
Electronic supplementary material The online version of this
article (doi:10.1007/s10870-008-9406-y) contains supplementary
material, which is available to authorized users.
X.-L. Zhang ꢀ Z.-T. Zhang ꢀ Y. Liang
Key Laboratory of Medicinal Plant Resources and Natural
Pharmaceutical Chemistry (Shaanxi Normal University),
Ministry of Education, Xi’an 710062,
People’s Republic of China
X.-L. Zhang ꢀ Z.-T. Zhang (&) ꢀ Y. Liang
School of Chemistry and Materials Science, Shaanxi Normal
University, Xi’an 710062, People’s Republic of China
e-mail: zhangzt@snnu.edu.cn
123

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J Chem Crystallogr (2008) 38:861–865
Scheme 1 The route of
synthesis for
[Na(H2O)2(C18H15O6SO3)]2
H3CO
H3CO
O
HO
O
C
1) H2SO4
A
(CH3)2SO4
KOH
H3CO
2) NaCl
B
OH
O
OH
O
OCH3
OCH3
H2O
OH2
CH3
Na1
1
O
8
5'
O
S
OH
O
OCH3
OCH3
O
2
3
O
6'
4'
7
O
H3CO
H3CO
S
A
C
B
1'
6
5
O
3'
4
2'
O
O
O
O
Na1
OH2
O
OH
H3C
H2O
Irisolidone (2.0 g) was dissolved into acetone (60 mL)
and KOH (2 mL, 0.3%). Dimethyl sulfate (2 mL) was
added dropwise to the solution with vigorous stirring at
room temperature for 4 h. The solution was poured into
water (60 mL), a pale yellow precipitation was appeared,
filtered, washed with water until the pH of the filtrate was
7. The dried yellow precipitation (1.8 g) was slowly added
to the concentrated sulfuric acid (9 mL), the mixture was
stirred at 40 °C for 30 min and poured into the saturated
NaCl solution (40 mL) to obtain a precipitate. After 2 h,
the precipitate was filtered and washed with saturated NaCl
solution until the pH value of the filtrate was 7. The pre-
cipitate was recrystallized from water to afford the title
compound (2.38 g) in good yield (85%). Yellow plate
single crystals suitable for XRD were grown in ethanol–
water (V:V, 1:1) solution by slow evaporation at room
temperature, m.p: 590 K(decomposed). IR (KBr) m: 3447,
2947, 1650, 1589, 1489, 1274, 1185, 1079, 828, 631, 550,
used for the diffraction study showed no decomposition
during data collection. Data collection detail and structure
determination results are summarized in Table 1. Selected
bond lengths and angles are presented in Table 2.
CCDC-294958 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or
from the Cambridge Crystallographic Data Centre
(CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; Fax:
+44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk].
Table 1 Crystal and structure refinement data for [Na(H2O)2
(C18H15O6SO3)]2
Formula
C36H38Na2O22S2
932.78
M
Crystal system
Space group
Monoclinic
P21/c (No. 14)
15.4591(4)
7.9523(3)
16.5859(5)
80.337(3)
2012.13(11)
2
1
489 cm-1. H NMR (DMSO-d6, 300 MHz, ppm) d: 3.74
˚
a (A)
0
(s, 3H, CH3O–C6), 3.81 (s, 3H, CH3O–C4 ), 3.93 (s, 3H,
˚
b (A)
CH3O–C7), 6.84 (s, 1H, H–C8), 7.05 (d, 1H, J = 8.5 Hz,
0
H–C5 ), 7.50 (dd, 1H, J = 8.4 Hz, J = 1.6 Hz, H-C6 ), 7.90
0
˚
c (A)
0
(d, 1H, J = 1.6 Hz, H–C2 ), 8.47 (s, 1H, H–C2), 12.99 (s,
b (°)
Volume (A )
3
˚
1H, HO-C5). Anal. Calc. for C36H38Na2O22S2: C, 42.29; H,
4.54. Found: C, 42.45; H, 4.43%.
Z
Dcalc (g cm-3
)
1.540
A single crystal with dimensions of 0.38 9 0.30 9
0.23 mm3 was chosen for XRD studies. The data were col-
lected with graphite monochromated Mo Ka radiation
l (mm-1
)
0.243
F(000)
968
˚
(k = 0.71073 A) on a Bruker Smart-1000 CCD diffrac-
Crystal size
0.38 9 0.30 9 0.23
4417/4/297
7137
tometer at room temperature. The structure was solved by
direct methods and refined on F2 by full matrix least-squares
with the Bruker’s SHELXL-97 program [14]. All non-
hydrogen atoms were refined anisotropically. H bonded to C
atoms were placed at calculated positions and treated as
Data/restraint/parameters
Reflections collected
Independent reflections
Goodness-of-fit
4417
1.008
R1 [I [ 2r (I)]
0.0415
˚
riding, with C–H distance in the range 0.93–0.96 A and Uiso
wR2 [I [ 2r (I)]
R1 (all data)
0.1068
(H) values of 1.2Ueq of the attached C atom [1.5Ueq (C) for
methyl H atoms]. H atoms of the water molecules were found
in difference maps and positionally refined with restraints of
0.0762
wR2 (all data)
-3
˚
Residuals (e A
0.1165
)
0.353, -0.432
˚
O–H = 0.85 (2) A and Uiso(H) = 1.5Ueq(O). The crystals
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J Chem Crystallogr (2008) 38:861–865
863
˚
Results and Discussion
Table 2 Selected bond distances (A) and angles (°) for
[Na(H2O)2(C18H15O6SO3)]2
The title compound is a dimeric centrosymmetric species and
the asymmetric unit consists of a cation Na+, a sulfonate of
¯
isoflavone anion C18H15O6SO3 and two coordinated water
Bond distances
Na1–O7
Na1–O11
Na1–O6#1
S1–O8
2.2547(11) Na1–O8#1
2.3193(14) Na1–O10
2.6365(13) S1–O7
1.4514(11) S1–O9
1.3624(16) O1–C1
1.3724(16) O5–C17
0.829(16) O11–H11A
1.4114(18) C14–C15
2.2965(12)
2.3576(16)
1.4426(10)
1.4530(10)
1.3478(16)
1.4316(19)
0.857(16)
1.3881(19)
0.9600
molecules (Fig. 1). The anion composed of a benzopyranone
moiety A(C11–C16)C(O5/C8–C12), a phenyl moiety B(C1–
C6) and a sulfonate monoanion. In the anion, the bond lengths
and bond angles of isoflavone skeleton are agreement with
those of [Na(H2O)](C17H13O6SO3) ꢀ 2H2O [15]. The atoms
of benzopyranone moiety are nearly coplanar, the dihedral
angle between ring A(C4–C9) and ring C(O1/C1–C4/C9) is
2.1°. To avoid steric conflicts, the two rigid ring systems,
phenyl ring B and benzopyranone moiety are rotated by 37.2°
with respect to each other. The similar S–O bond lengths and
bond angles involving O7, O8 and O9 show that the negative
charge is delocalized over the three oxygen atoms [1].
O6–C13
O1–C9
O10–H10A
C12–C13
C14–H14
0.9300
C18–H18A
Bond angles
O7–S1–O8
113.00(7)
111.96(7)
122.19(5)
83.84(4)
O7–S1–O9
112.30(6)
O8–S1–O9
O8#1–Na1–O10
O11–Na1–O10
S1–O7–Na1
100.60(5)
89.34(5)
164.36(8)
109.5
O7–Na1–O11
O7–Na1–O6#1
C7–O5–C17
Na1–O10–H10A
C11–C12–C13
C9–C4–C5
Each Na(I) is five-coordinated by O6#1 from methoxy,
O7 and O8#1 from sulfo-group, O10 and O11 from coordi-
nate water molecules [symmetry code: #1 (-x, -y, 1 - z)],
the Na–O bond lengths fall in the range of 2.2547(11)–
117.88(12)
112.9(18)
119.77(12)
117.56(12)
C5–O3–H3
Na1–O11–H11A
O1–C1–C2
117.4(16)
125.96(13)
H17A–C17–H17B 109.5
˚
2.6365(13) A. The coordination polyhedron may be descri-
Symmetry code: #1: -x, -y, 1 - z
bed as a distorted trigonal bipyramidal geometry.
Fig. 1 ORTEP diagram of the
dimeric
[Na(H2O)2(C18H15O6SO3)]2
(with 40% probability
ellipsoids), the hydrogen atoms
were omitted for clarity.
Symmetry code: #1 (-x, -y,
1 - z)
Fig. 2 C–H_p and C–H_O
hydrogen bonds link the
ꢀ
molecules to form a [0 2 2]
sheet. Symmetry code:
#2 (1 - x, y - 0.5, 0.5 - z);
#3 (1 - x, -y, 1 - z)
123

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J Chem Crystallogr (2008) 38:861–865
Fig. 3 The dimeric units are interconnected by the two kinds of synthons R22 (8) and R22 (12). (a) R22 (8) ring and (b) R22 (12) ring. Symmetry
code: #1 (-x, -y, 1 - z); #4 (-x, 1 - y, 1 - z); #5 (x, y + 1, z)
Figure 2 shows the hydrogen-bonded sheet structure of
the title compound wherein the dimeric units are inter-
connected by C–Hꢀꢀꢀp and C–HꢀꢀꢀO hydrogen bonds. Two
adjacent dimeric units are linked through two C–Hꢀꢀꢀp
hydrogen bonds. Atom C1 acts as a hydrogen-bond donor,
via the atom H1, to the CgA#2 [Symmetry code: #2 (1 - x,
y - 0.5, 0.5 - z)], to form a C–Hꢀꢀꢀp (arene) hydrogen
bond. Meanwhile, CgB acts as a hydrogen-bond acceptor,
via the atom H17A#2, from C17#2 to form the other
C–Hꢀꢀꢀp (arene) hydrogen bond, where CgA#2 and CgB are
the centers of ring A (C4–C9) at (1 - x, y - 0.5, 0.5 - z)
and ring B (O1/C1–C4/C9) in the molecule at (x, y, z),
respectively. The dimer interacts with the other via paired
intermolecular hydrogen bonds C18–H18AꢀꢀꢀO5 which
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J Chem Crystallogr (2008) 38:861–865
865
Fig. 4 3D supramolecular network of the title compound
˚
the electrostatic interactions between the cation and the
anion result in the 3D framework structure as illustrated in
Fig. 4.
Table 3 Typical hydrogen bond distances (A) and angles (°) in
[Na(H2O)2(C18H15O6SO3)]2
D–HꢀꢀꢀA
D–H
HꢀꢀꢀA
DꢀꢀꢀA
D–H–A
O3–H3ꢀꢀꢀO2
0.82
1.81
2.5426(15) 148.7
Acknowledgments We thank the Science and Technology Key
Project of Education Ministry, P. R. China (No: 107138) for financial
support.
O10–H10AꢀꢀꢀO9
O11–H11AꢀꢀꢀO8
O10–H10BꢀꢀꢀO4
O11–H11BꢀꢀꢀO9
C18–H18AꢀꢀꢀO5
C1–H1ꢀꢀꢀO3
0.829(16) 2.020(16) 2.8458(16) 174(2)
0.857(16) 2.065(16) 2.9153(17) 171(2)
0.794(16) 2.259(19) 2.9578(16) 147(2)
0.834(16) 2.065(16) 2.8988(16) 178(2)
References
0.96
0.93
0.93
2.58
2.35
2.95
2.88
3.467(2)
154.2
3.1304(17) 141.4
3.2618(16) 101
3.5025(19) 124
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