Synthesis, Structure and Biological Activity of a Ca(II)
Coordination Polymer with Pyrazole-3,5-dicarboxylate as Ligand
Tai Xi-Shi1,*, Jia Zong-Qing2 and Wang Xin3
1College
of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, P. R. China
2Shouguang Fukang Pharmaceutical Co. Ltd, Shouguang 262700, P. R. China
3Deaprtment of Chemistry, Qinghai Normal University, Xining 810008, P.R. China
ABSTRACT: Using pyrazole-3,5-dicarboxylic acid and Ca(ClO4)2·H2O as materials, a
novel Ca(II) coordination polymer, {[Ca(L)(H2O)4]·(H2O)}n (1) was synthesized and characterized. The results reveals that Ca(II) complex forms 1D chained structure. The 1D
chain further formed a three-dimensional network structure by π-π stacking interaction.
The antitumor effect of complex 1 against three human tumor cells has been investigated.
INTRODUCTION
M
complex materials have shown many
good applications in magnetics, catalysis, fluorescence, antimicrobial and antitumor activities [1–6].
However, the studies on the structures and applications
of alkaline earth metal complex are very rare compared
with the d metal complex materials [7–13]. In the previous work of our group, some Mg(II) and Ca(II) complexes have been reported [14–16]. As the continue
work of our group, herein, we report the spectral characterization, crystal structure and antitumor activity of
a novel Ca(II) coordination polymer.
etal
in 20 mL CH3CH2OH/H2O (v:v = 5:1). Then 0.1190
g Ca(ClO4)2·H2O (1.0 mmol) was added and refluxed
for 5 h with stirring. The colorless crystals were obtained from the filtrate after 30 days. Yield: 71%. Anal.
Calcd. (%) for C5H12CaN2O9: C, 21.11; H, 4.22; N,
9.85. Found (%): C, 21.42; H, 4.78; N, 9.67. IR max
(cm–1): 2987 cm–1, 1666 cm–1, 1506 cm–1, 1425 cm–1,
1277 cm–1, 1242 cm–1, 1203 cm–1, 750 cm–1.
Crystal Data and Structure Refinement
EXPERIMENTAL
The crystal data for complex 1 are given in Table
1. SHELXL-97 [17] was used to solve and refine the
structure. Molecular graphics was drawn with SHELXTL-97 [18].
Materials and Methods
Results and Discussion
Ca(ClO4)2·H2O, pyrazole-3,5-dicarboxylic, sodium
hydroxide were used to synthesize. Elemental analyses
for C, H and N were carried out on a Elementar Vario
III EL elemental analyzer. Infrared spectrum (KBr,
4000–400 cm–1) was recorded using a Nicolet AVATAR 360 FT-IR spectrophotometer. Thermal analysis
was performed on a Shimadzu PT-40. The crystal data
was collected on a Bruker Smart CCD Area Detector.
The coordination mode of Ca(II) atom in 1 is shown
in Figure 1. The carboxylate groups of pyrazole-3,5dicarboxylate in 1 adopt bidentate coordinated mode.
The complex molecule contains one Ca(II) ion, one
pyrazole-3,5-dicarboxylate ligand, four coordinated
H2O molecules and one lattice H2O molecule. The
Ca(II) center is eight-coordinated, and forms a distorted double cap three prism geometry defined by
three O atoms from two pyrazole-3,5-dicarboxylate
anions, one N atom from one pyrazole-3,5-dicarboxylate anions, and four O atoms from four coordinated
H2O molecules. The bond lengths of Ca1-O4, Ca1-O3,
Ca1-O5, Ca1-O8, Ca1-O6, Ca1-O7 and Ca1-O4A are
2.3805(14) Å, 2.4081(16) Å, 2.4273(17) Å, 2.4464(17)
Å, 2.4636(16) Å, 2.4714(15) Å and 2.6016(14) Å, re-
Synthesis of {[Ca(L)(H2O)4]·(H2O)}n (1)
0.139 g pyrazole-3,5-dicarboxylic (1.0 mmol) and
0.08 g sodium hydroxide (2.0 mmol) were dissolved
*Author to whom correspondence should be addressed.
E-mail: [email protected]; Tel.: +86-536-8785363
Journal of Residuals Science & Technology, Vol. 14, No. 1—January 2017
1544-8053/17/01 047-04
© 2017 DEStech Publications, Inc.
doi:10.12783/issn.1544-8053/14/1/6
47
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T. Xi-Shi, J. Zong-Qing and W. Xin
Table 1. Crystal Data for Title Compound 1.
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
γ/°
Volume/Å3
Z
ρcalcmg/mm3
μ/mm–1
S
F(000)
Index ranges
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indexes [I ≥ 2σ (I)]
Final R indexes [all data]
Largest diff. peak/hole/e Å–3
C5H12CaN2O9
284.25
293(2)
Monoclinic
P21/c
7.7311(6)
15.6179(12)
9.3350(7)
90.00
96.6980(10)
90.00
1119.45(15)
4
1.687
0.603
1.062
592
–7 ≤ h ≤ 10, –20 ≤ k ≤ 20, –12 ≤ l ≤ 12
6973
2658 [R(int) = 0.0551]
2658/10/194
1.064
R1 = 0.0402, wR2 = 0.1080
R1 = 0.0425, wR2 = 0.1094
0.420/–0.701
spectively. The average bond length of Ca-O is 2.4570
Å. The bond length of Ca1-N1 is 2.6574(17) Å. The 1
molecule forms 1D chained structure by the bridging
effect of carboxylate groups of pyrazole-3,5-dicarboxylate (Figure 2), and the 3D framework structure also
forms though the interaction of 1D chains (Figure 3).
The 1 molecule forms 1D chained structure by the interaction of hydrogen bonds.
Figure 1. The coordination mode of Ca(II).
IR Spectra and Thermal Analyses
Complex 1 displays the strong bands at ca. 1666
cm–1 and 1425 cm–1 in the IR spectrum, respectively,
which may be attributed to the stretching vibrations
of carboxylic group [19]. Which indicates that the O
atoms of pyrazole-3,5-dicarboxylic ligand take part in
coordination with Ca(II) atom. The Ca(II) coordination
polymer has three weight loss steps in the thermal analysis: the first one appears at 98°C corresponding to the
removal of lattice water molecule (found 7.28%, calcd
6.33%). The second one is ascribed to the loss of coordinated water molecules between 162°C and 196°C.
The third one shows a continuous weight loss from 196
to 402°C due to the decomposition of pyrazole-3,5-dicarboxylic ligand. The above results indicate that the
Ca(II) coordination polymer contains water molecules,
which is in agreement with the elemental analysis results.
Figure 2. The 1D chained structure of 1 by bridging effect of carboxylate groups.
Synthesis, Structure and Biological Activity of a Ca(II) Coordination Polymer with Pyrazole-3,5-dicarboxylate
49
Figure 3. The 3D network structure of 1.
Antitumor Activities
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The antitumor activities of complex 1 against three
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literature method [20]. The results indicated that it
showed excellent antitumor effect (IC50 = 18 ± 0.5 μg/
mL) against human lung adenocarcinoma A549 cells.
However, it does not show antitumor effect against the
other two human tumor cells.
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CONCLUSIONS
A novel Ca(II) coordination polymer, {[Ca(L)
(H2O)4]·(H2O)}n has been synthesized and structural
characterized. The molecules form 1D chained structure by the bridging effect of carboxylate groups of
L ligands. The antitumor activities indicated that it
showed excellent antitumor effect against human lung
adenocarcinoma A549 cells. Based on these, more and
more Ca(II) coordination polymers will be synthesize
to investigate their novel structures and antitumor activities.
ACKNOWLEDGMENTS
The authors would like to thank the National Natural Science Foundation of China (No. 21171132),
the Natural Science Foundation of Shandong (ZR2014BL003), and the Project of Shandong Province
Higher Educational Science and Technology Program
(J14LC01) and Science Foundation of Weifang.
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