Synthesis and crystal structure of hydrate adduct of 6-benzylaminopurine and 5-sulfosalicylic acid [(C12H12N5)(C 7H5O6S).H2O]

Article abstract of DOI:10.1007/s10870-010-9709-7

The crystal structure of hydrate adduct of 6-benzylaminopurine and 5-sulfosalicylic acid [(C¹²H¹²N⁵) (C ⁷H⁵O⁶S).H²O] 1 is studied. It crystallizes in monoclinic system space grou

Full text of DOI:10.1007/s10870-010-9709-7

J Chem Crystallogr (2010) 40:634–638
DOI 10.1007/s10870-010-9709-7
ORIGINAL PAPER
Synthesis and Crystal Structure of Hydrate Adduct
of 6-Benzylaminopurine and 5-Sulfosalicylic Acid
[(C12H12N5)(C7H5O6S)ÁH2O]
•
Min Xia Kui-Rong Ma Yulan Zhu
•
Received: 9 November 2009 / Accepted: 16 January 2010 / Published online: 4 February 2010
Ó Springer Science+Business Media, LLC 2010
Abstract The crystal structure of hydrate adduct of
6-benzylaminopurine and 5-sulfosalicylic acid [(C12H12N5)
(C7H5O6S)ÁH2O] 1 is studied. It crystallizes in monoclinic
regulation, stress resistance, anti-aging and anti-heavy
metal pollution, etc. Metal ions in life processes can lead to
body lesions, so the research of the complexation reaction
of purine compounds with metal ions has an important
significance in the life sciences [1–4]. Up to date, there are
few reports on the 6-benzyl-amino-purine derivative. In
this paper, we introduce a hydrate adduct of 6-benzyl-
aminopurine and 5-sulfosalicylic acid [(C12H12N5)(C7H5
O6S)ÁH2O] 1, in which there are lots of the strong hydrogen
bonds and p–p interactions. Its structure was determined
using the X-ray diffraction method and characterized with
spectroscopic techniques.
˚
system space group P21/n with a = 6.2128(9) A, b =
˚
˚
20.762(3) A, c = 15.675(2) A, b = 92.040(2)°, V =
3
2
˚
2,020.6(5) A , Z = 4, Rgt(F) = 0.0494, wRref(F ) = 0.1112,
and T = 173(2) K. Single-crystal X-ray diffraction analy-
sis reveals that the asymmetric unit of 1 contains one
6-benzylaminopurine molecule and one 5-sulfosalicylic
acid molecule, as well as one lattice water molecule. In 1,
hydrogen bonds link the two monomers into one-dimen-
sional double chain, two-dimensional layer network, and
further a 3-D supramolecular network. Short ring-interac-
tions with intra-chain p–p stacking are observed (distances
˚
between ring centroids are 3.964, 3.796 and 3.571 A, and
Experimental Section
the dihedral angle between planes are 6.97°, 5.55°, and
5.66°, respectively).
General Procedures and Materials
Keywords Crystal structure Á 6-Benzylaminopurine Á
3-D supramolecular network Á p–p Conjugate effects
All chemicals purchased were reagent grade and used
without further purification. IR spectrum was recorded
on an AVATAR360 spectrophotometer with range 4,000–
400 cm-1 using KBr pellets. Elemental analyses were
performed using an Optima-2000DV elemental analyzer.
Introduction
6-Benzylaminopurine (6-BA) is the type of adenine
derivative with 6-substituted group. 6-benzyl-amino sub-
stituent has a higher activity, which made it play an
important role in the tissue culture, gene expression
Synthesis of Hydrate Adduct of 1
Compound 1 was synthesized by the reaction of 6-ben-
zylaminopurine 0.0226 g (0.1 mmol) and 5-sulfosalicylic
acid 0.05 g (0.2 mmol) in methanol 8 mL. Mixture was
placed in a 15 mL test tube for 10 days at room tempera-
ture. The crystalline of 1 (colorless club-shaped) was col-
lected by vacuum filtration and dried in air (yield 53%).
Elemental analysis calcd. for C19H25N5O7S (%): C
49.41, H 4.12, N 15.17, O 24.27; Found: C 49.39, H 4.08,
O 24.31, N 15.22. IR data (cm-1): 3403(w), 3131(w),
M. Xia (&) Á K.-R. Ma Á Y. Zhu
Jiangsu Key Laboratory for Chemistry of Low-Dimensional
Materials, School of Chemistry and Chemical Engineering,
Huaiyin Normal University, 223300 Huaian, Jiangsu,
People’s Republic of China
e-mail: xiamin@hytc.edu.cn
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J Chem Crystallogr (2010) 40:634–638
635
3031(w), 1749(w), 1724(m), 1658(s), 1610(m), 1475(w),
1398(m), 1353(w), 1234(w), 1174(s), 1124(m), 1079(w),
1035(s), 885(w), 840(w), 784(w), 721(w), 665(w), 593(m),
484(w).
X-ray Structure Determination of 1
The crystal and instrumental parameters used in the unit-
cell determination and data collection are summarized in
Table 1. Diffraction measurements were made at room
temperature on a Bruker SMART APEX II X-ray diffrac-
tometer using graphite-monochromated Mo Ka radiation
using x/2h scan mode. Unit-cell dimensions were deter-
mined and refined in the 1.96° \ h \ 26.00° range. The
structure was solved by the direct methods using SHELXS-
97 and refined by full-matrix least-squares techniques
on F2 with SHELXL-97 [5, 6]. The empirical absorption
corrections were applied by the multi-scan method via
X-RED software. All non-hydrogen atoms were refined
with anisotropic displacement parameters and hydrogen
atoms were included in their idealized positions and refined
isotropically. ORTEP drawing [7] of the molecule with
50% probability displacement thermal ellipsoids and atom-
Fig. 1 ORTEP drawing of the molecule with 50% probability
displacement thermal ellipsoids
labeling scheme are shown in Fig. 1. Selected bond dis-
˚
tances (A) and angles (°) for compound are list in Table 2.
Results and Discussion
Description of the Crystal Structure of Hydrate Adduct
of 6-Benzylaminopurine and 5-Sulfosalicylic Acid
[(C12H12N5)(C7H5O6S)ÁH2O] 1
Table 1 Crystal data and structure refinement for 1
CCDC no.
753471
19H19N5O7S
Empirical formula
Formula weight
T (K)
C
Single-crystal X-ray diffraction analysis reveals that the
asymmetric unit of 1 contains one 6-benzylaminopurine
molecule and one 5-sulfosalicylic acid molecule, as well as
one lattice water molecule (Fig. 1). The exocyclic bond
length C(3)–C(7) and C(13)–C(14) are elongated to
461.45
173 (2)
˚
Radiation (k, A)
Mo Ka (0.71073)
Monoclinic, P21/n
Crystal system, space group
˚
Unit cell dimensions (A, °)
˚
1.466(4) A and 1.498(3) A, longer than the cyclic those of
˚
a
b
c
6.2128(9)
20.762(3)
15.675(2)
92.040(2)
4
˚
C–C bonds (average 1.388 A). The bond lengths N–C
˚
are average 1.349 A, except for exocyclic N(5)–C(11)
˚
(1.313(3) A) and N(5)–C(13) (1.475(3) A). The C(4)–O(6)
˚
b
Z
˚
bond length (1.351(3) A) is long than C(7)–O(4) and
˚
˚
C(7)–O(5) bond lengths (1.250(3) A and 1.293(3) A,
3
˚
V (A )
2,020.6(5)
1.517
˚
respectively). The bond lengths S–O are average 1.454(2) A.
Dcalc. (g cm-1
)
The molecular unit 1 as a whole, ignoring the lattice
water molecule, contains three six-membered rings and
one five-membered ring, N1–C8–N2–C9–C10 marked P1,
N3–C11–C10–C9–N4–C12 marked P2, C14–C15–C16–
C17–C18–C19 marked P3 and C1–C2–C3–C4–C5–C6
marked P4. The one 6-benzylaminopurine molecule and
one 5-sulfosalicylic acid molecule, join together through
hydrogen bonds. The corresponding hydrogen bonds are
l (mm-1
)
0.215
F(000)
960
Crystal size (mm)
0.30 9 0.25 9 0.15
1.96–26
h Range for data collection (°)
Index ranges
-7 B h B 7, -25 B k B 22,
-19 B l B 19
Reflections/unique (Rint
Data/parameters
)
14785/3920 (Rint = 0.0670)
3920/295
˚
O(5)–H(5A)ÁÁÁN(1) (2.553 A, 169.0°), N(5)–H(5B)ÁÁÁO(4)
R indices [I [ 2r(I)]
Goodness of fit indication
R1 = 0.0494, wR2 = 0.1112
1.021
˚
(2.877 A, 168°) and intra-hydrogen bond O(6)–H(6A)ÁÁÁ
˚
O(4) (2.619 A, 146°). The molecular units (1)n, as a basic
building unit, are connected with each other by hydrogen
Largest difference peak
-3
0.294 and -0.368
˚
and hole (e A
)
˚
bonds, N(3)–H(3)ÁÁÁO(1) (2.763 A, 148.0°), C(12)–H(12)ÁÁÁO(3)
123

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J Chem Crystallogr (2010) 40:634–638
˚
Table 2 Selected bond lengths (A) and angles (°) for 1
C(1)–C(2)
1.380(3)
1.395(3)
1.380(3)
1.392(3)
1.406(3)
1.466(4)
1.351(3)
1.385(4)
1.380(4)
1.408(3)
1.767(3)
119.3(2)
119.29(2)
121.3(2)
121.2(2)
118.9(2)
119.9(2)
121.1(2)
118.2(2)
122.1(2)
119.7(2)
120.5(2)
120.3(2)
123.2(2)
121.8(2)
115.0(2)
121.1(3)
C(7)–O(4)
1.250(3)
1.293(3)
1.323(3)
1.344(3)
1.352(3)
1.355(3)
1.377(3)
1.313(3)
1.372(3)
1.300(3)
1.369(3)
112.7(2)
126.4(2)
105.8(2)
127.8(2)
110.1(2)
131.4(2)
118.6(2)
121.6(2)
125.7(2)
112.7(2)
125.5(3)
111.4(2)
118.7(2)
121.2(2)
120.1(2)
C(13)–N(5)
1.475(3)
1.498(3)
1.377(4)
1.404(4)
1.382(4)
1.382(4)
1.378(4)
1.384(4)
1.4669(2)
1.4473(2)
1.4475(2)
120.0(3)
119.9(3)
120.2(3)
120.2(3)
104.0(2)
107.3(2)
123.8(2)
111.6(2)
123.8(2)
113.81(1)
111.28(1)
112.44(1)
106.73(1)
106.67(1)
105.25(1)
C(1)–C(6)
C(7)–O(5)
C(13)–C(14)
C(9)–C(10)
C(8)–N(1)
C(14)–C(15)
C(2)–C(3)
C(8)–N(2)
C(14)–C(19)
C(3)–C(4)
C(9)–N(2)
C(15)–C(16)
C(3)–C(7)
C(9)–N(4)
C(16)–C(17)
C(4)–O(6)
C(10)–N(1)
C(17)–C(18)
C(4)–C(5)
C(11)–N(5)
C(18)–C(19)
C(5)–C(6)
C(11)–N(3)
O(1)–S(1)
C(10)–C(11)
C(1)–S(1)
C(12)–N(4)
O(2)–S(1)
C(12)–N(3)
O(3)–S(1)
C(2)–C(1)–C(6)
C(2)–C(1)–S(1)
C(6)–C(1)–S(1)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(2)–C(3)–C(7)
C(4)–C(3)–C(7)
O(6)–C(4)–C(5)
O(6)–C(4)–C(3)
C(5)–C(4)–C(3)
C(6)–C(5)–C(4)
C(5)–C(6)–C(1)
O(4)–C(7)–O(5)
O(4)–C(7)–C(3)
O(5)–C(7)–C(3)
C(14)–C(15)–C(16)
N(1)–C(8)–N(2)
N(2)–C(9)–N(4)
N(2)–C(9)–C(10)
N(4)–C(9)–C(10)
N(1)–C(10)–C(9)
N(1)–C(10)–C(11)
C(9)–C(10)–C(11)
N(5)–C(11)–N(3)
N(5)–C(11)–C(10)
N(3)–C(11)–C(10)
N(4)–C(12)–N(3)
N(5)–C(13)–C(14)
C(15)–C(14)–C(19)
C(15)–C(14)–C(13)
C(19)–C(14)–C(13)
C(15)–C(16)–C(17)
C(18)–C(17)–C(16)
C(17)–C(18)–C(19)
C(18)–C(19)–C(14)
C(8)–N(1)–C(10)
C(8)–N(2)–C(9)
C(12)–N(3)–C(11)
C(12)–N(4)–C(9)
C(11)–N(5)–C(13)
O(2)–S(1)–O(3)
O(2)–S(1)–O(1)
O(3)–S(1)–O(1)
O(2)–S(1)–C(1)
O(3)–S(1)–C(1)
O(1)–S(1)–C(1)
˚
˚
(3.220 A, 155.0°), C(13)–H(13A)ÁÁÁO(3) (3.445 A, 148.0°)
interactions are best propitious to stabilize the structure, as
well charge transfer [8–10]. As a sequential work, we now
further consider the new studies with other substituents and
investigate effect on the biological activity derived of inter-
and/or intramolecular interactions.
˚
and C(15)–H(15)ÁÁÁO(1) (3.478 A, 157.0°), to extend into a
1-D double chain along the b-axis (Fig. 2). The structure of
1 extends from 1-D double-chain to 2-D supramolecular
layer under the interactions of hydrogen bonds in the bc
plane (Fig. 3). The corresponding hydrogen bond distance
The UV–visible absorption spectrum of 1 in ethanol is
shown in Fig. 5. The bands centered at 270.9 and
334.9 nm. Result reveals that the absorption band
270.9 nm is red-shifted due to the protonation character of
6-BAP, in comparison to that of the parent 6-BAP
(267.5 nm), but the above 334.9 nm may be much more
likely resulted in p–p conjugation effect.
IR spectrum of the compound 1 was recorded in the
4,000–400 cm-1 region (Fig. 6). The bands centered at
3,403 cm-1 (N–H and O–H), 3,243 cm-1 (N–H) and
3,131 cm-1 (N–H) could be assigned to N–H and O–H
stretching vibrations, which peaks shifted towards lower
wavenumber under the information of the hydrogen-
bonding and/or p–p conjugation effect, comparing with
free 6-BAP (3,444, 3,257, 3,207 cm-1) and free –OH
(about 3,650 cm-1) [11]. The band located at 3,031 cm-1
˚
and angle, C(8)–H(8)ÁÁÁO(2), are 3.240 A and 132.0°.
Within layer, the weak p–p packing interactions in face-to-
face for P2-P3 and P4-P1 and offset face-to-face for P1-P3
˚
(distance between rings centroids are 3.964/3.796 A and
˚
3.571 A, and the dihedral angle are 6.97°/5.55° and 5.66°,
respectively), further reinforce supramolecular structural
stability. At last, a 3-D supramolecular network is further
constructed via hydrogen bonds C(17)–H(17)ÁÁÁO(3)
˚
˚
(3.496 A, 163.0°) and C(19)–H(19)ÁÁÁO(6) (3.387 A,
161.0°), as well as hydrogen bonds formed by lattice water
molecules (Fig. 4). The parameters of the hydrogen bonds
are listed in Table 3.
The packing diagram of 1 (Fig. 3) shows the stronger
p–p conjugate effects stacking in face-to-face and offset
face-to-face alignment mode along the x-axis. The stacking
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J Chem Crystallogr (2010) 40:634–638
637
˚
Table 3 Intra- and inter-molecular hydrogen bond distances (A) and
angles (°) for 1
D–HÁÁÁA
d(D–H)
d(HÁÁÁA)
d(DÁÁÁA)
\(DHA)
N2–H2AÁÁÁO7#1
N3–H3ÁÁÁO1#2
O5–H5AÁÁÁN1#1
N5–H5BÁÁÁO4#3
O6–H6AÁÁÁO4
O7–H7AÁÁÁO1#4
O7–H7BÁÁÁO2#5
C8–H8ÁÁÁO2
C12–H12ÁÁÁO3#2
C13–H13AÁÁÁO3#6
C15–H15ÁÁÁO1#6
C17–H17ÁÁÁO3#7
C19–H19ÁÁÁO6
0.8800
0.8800
0.8300
0.8800
0.8300
0.8300
0.8700
0.9500
0.9500
0.9900
0.9500
0.9500
0.9500
1.8200
1.9800
1.7400
2.0100
1.8900
2.0300
2.0500
2.5300
2.3400
2.5700
2.5800
2.5800
2.4800
2.6895
2.7631
2.5534
2.8769
2.6188
2.8272
2.8258
3.2404
3.2203
3.4450
3.4782
3.4957
3.3867
171.00
148.00
169.00
168.00
146.00
160.00
148.00
132.00
155.00
148.00
157.00
163.00
161.00
Fig. 2 The 1-D hydrogen-bonded double chain of 1 along the b-axis.
Hydrogen bonds are drawn as blue dotted lines. (Color figure online)
Symmetry transformations used to generate equivalent atoms: #1 x -
1, y, z #2 -x ? 1/2, y-1/2, -z ? 3/2 #3 x ? 1, y, z #4 -x ? 1,
-y ? 2, -z ? 1 #5 -x ? 2, -y ? 2, -z ? 1
Fig. 3 The 2-D hydrogen-bonded layer of 1 in the bc plane, as well
as p–p interactions. Hydrogen bonds are drawn as blue dotted lines.
(Color figure online)
Fig. 5 UV–vis absorption spectrum of 1 in ethanol at room
temperature. Inset UV-vis spectrum of 6-BAP in ethanol at room
temperature
Fig. 4 The 3-D supramolecular network built from hydrogen bonds.
Hydrogen bonds are drawn as blue dotted blue lines. (Color figure
online)
could be assigned to C–H stretching vibration of aromatic
ring. The asymmetric and symmetric stretching vibra-
tions of the carboxyl group are centered at 1,724 and
Fig. 6 IR spectrum of 1
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J Chem Crystallogr (2010) 40:634–638
1,398 cm-1, respectively. The bands observed between
1,658 and 1,610 cm-1 may be assigned to the C–N
stretching vibrations of the heterocyclic ring. The bands
from 1,234 to 1,035 cm-1, can be attributed to the
stretching vibrations of the S=O and S–O groups,
respectively.
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