Synthesis, crystal structure and antibacterial activity of Ca(II) complex with 2-(Phenylsulfonamido)acetic acid

Article abstract of DOI:10.14233/ajchem.2013.13233

A new ligand 2-(phenylsulfonamido)acetic acid (L) and its Ca(II) complex have been synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The results showed that the complex formed one dimensional chaine

Full text of DOI:10.14233/ajchem.2013.13233

Asian Journal of Chemistry; Vol. 25, No. 4 (2013), 1913-1916
http://dx.doi.org/10.14233/ajchem.2013.13233
Synthesis, Crystal Structure and Antibacterial Activity of Ca(II)
Complex with 2-(Phenylsulfonamido)acetic Acid
*
TAI XI-SHI , CHU SI-YUAN and TANG CHUN-YING
College of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, P.R. China
*Corresponding author: Fax: +86 536 8785363; Tel: +86 536 8785363; E-mail: taixs@wfu.edu.cn
(Received: 12 December 2011;
Accepted: 8 October 2012)
AJC-12249
A new ligand 2-(phenylsulfonamido)acetic acid (L) and its Ca(II) complex have been synthesized and characterized by elemental analysis,
IR spectroscopy and single-crystal X-ray diffraction. The results showed that the complex formed one dimensional chained structure
through intramolecule and intermolecule hydrogen bonds and π-π stacking. The antibacterial assay of the Ca(II) complex and the lignd L
was tested using a modified version of 2-fold serial dilution method. The Ca(II) complex shows considerable antibacterial activity against
Escherichia coli, Bacillus subtilis and Staphylococcus white.
Key Words: 2-(Phenylsulfonamido)acetic acid, Ca(II) complex, Crystal structure, Antibacterial activity.
by X-ray single crystal diffraction, indicating that the complex
formed one-dimensional chain structure. The antibacterial
assay of the Ca(II) complex was tested using a modified version
of the 2-fold serial dilution method.
INTRODUCTION
Calcium is the indispensable element in biology. It is
involved in several biochemical processes and is the essential
cofactor required for the activation of a variety of enzymes. In
the process of metabolism, calcium ions possess of a variety
of coordination structures and play an important role in
catalysis. It can be as the enzyme activator and bridged the
adjacent carboxylates to strengthen the cell membrane in the
lipoprotein1-3. In eucaryotes, calcium ions are involved in
regulation of dozens of processes, such as mitosis, muscle
contraction, proliferation and coagulation of blood, hormone
secretion and differentiation in different types of cells. In
addition, it also plays an integrating role in controlling coor-
dinated function of different compartments, cells and organs.
Thus, it is referred to the metal of life4-6. It is significant to
study7 on the structure and characteristic coordination of cal-
cium for making sure about physiological and biochemical
mechanisms of all lives.
Aromatic compounds with carboxylic acid are affluent in
the coordination structures8,9, their complexes are important
for academic significance, but also possess potential application
and prospect in many areas, such as material, biochemistry,
medicinal preparation, catalytic behavior, micro-porosity, elec-
trical conductivity, non-linear optical activity and cooperative
magnetic behavior10-14. Herein, a novel calcium complex was
synthesized by the reaction of calcium perchlorate tetrahydrate
with 2-(phenylsulfonamido)acetic acid and was characterized
EXPERIMENTAL
The following AR grade chemicals were used for the
preparation of the studied compound: calcium perchlorate
tetrahydrate, benzenesulfonyl chloride, glycine, sodium
hydroxide.
The carbon, hydrogen and nitrogen content in the newly
synthesized compound were determined on a Elementar Vario
III EL elemental analyzer. Infrared spectrum (4000-400 cm-1)
was recorded with KBr optics on a NicoletAVATAR 360 FTIR
spectrophotometer. The crystal data was collected on a Bruker
smart CCD Area Detector.
Synthesis of the ligand: 10 mmol (0.7507 g) of glycine
and 20 mmol (0.8 g) of sodium hydroxide were dissolved in
100 mL of water at room temperature and added drop by drop
10 mmol (1.7662 g) of benzenesulfonyl chloride by stirring at
room temperature. The reaction solution was kept running for
4 h, then acidified with the solution of hydrochloric acid (v:v
= 1:1) to pH = 2. The white solid precipitation were collected
by filtration, washed and dried under vacuum.Yield may reach
up to over 65 %. Elementary analysis: calcd. (%) for
C8H9NSO4: C, 44.65; H, 4.19; N, 6.51; found (%): C, 44.58;
H, 4.52; N, 6.59. IR (KBr, νmax, cm-1): (C=O): 1718, (N-H):
3248 (Fig. 1).

1914 Xi-Shi et al.
Asian J. Chem.
O
S
O
TABLE- 1
CRYSTALLOGRAPHIC DATA FOR Ca(II) COMPLEX
H
N
COOH
H2N
COOH
S
Cl
+
O
O
Formula
Formula weight
C24H24N3O12S3CaNa
705.71
Fig. 1. Synthesis and structure of 2-(phenylsulfonamido)acetic acid
Crystal system
Space group
Monoclinic
P21/n
a (Å)
b (Å)
c (Å)
α (º)
β (º)
γ (º)
Z
F(000)
17.406(2)
8.7089(10)
20.069(3)
90.00
104.088(2)
90.00
4
1456
298(2)
2950.8(6)
1.589
Synthesis of Ca(II) complex: 1 mmol (0.215 g) of
2-(phenylsulfonamido)acetic acid and 1 mmol (0.04 g) of
sodium hydroxide were added to the 10 mL of CH3OH/H2O
(v:v = 2:1) solution.After being dissolved, 0.5 mmol (0.138 g)
of calcium perchlorate tetrahydrate was added to the solution.
The mixture was continuously stirred for 3 h at refluxing
temperature. The mixture was cooled at room temperature and
was collected by filtration. By evaporation in air at room tempe-
rature, the single crystal suitable for X-ray determination was
obtained from methanol solution after 10 days. Yield: 56 %.
Elementary analysis: calcd. (%) for C24H24N3O12S3CaNa: C,
40.85; H, 3.43; N, 5.95; found (%): C, 40.58; H, 3.69; N, 5.72.
IR (KBr, νmax, cm-1): (C=O): 1677, (N-H): 3248, (H2O): 3423.
X-Ray crystallography:A colourless block single crystal
with dimensions of 0.49 mm × 0.46 mm × 0.40 mm was placed
on a glass fiber and mounted on a CCD area detector. Diffrac-
tion data were collected by φ~ω scan mode using a graphite-
monochromatic MoKα radiation (λ = 0.71073 Å) at 298 (2)
K. A total of 14432 reflections were collected in the range
1.39-25.01º, of which 5190 were unique (Rint = 0.045) and
3866 were observed with I > 2σ(I). The data were corrected
for Lp factors. The structure was solved by direct methods
and refined by full-matrix least-squares techniques on F2. The
structure was solved by direct methods15 using SHELXL-97
and expanded using Fourier techniques. All non-hydrogen
atoms and hydrogen atoms were refined anisotropically and
isotropically, respectively. The final refinement by full-
matrix least squares method was converged at R = 0.041 and
wR = 0.1166 (w = 1/[δ2(Fo2) + (0.0507P)2 + 2.4758P], P =
(Fo2 + 2Fc2)/3 , S = 1.055, (∆/σ)max = 0.001). The largest peak
in the final difference Fourier map is 0.512 e/Å3 and the mini-
mum peak is -0.513 e/Å3. Molecular graphics were drawn with
the program package SHELXTL-97 crystallographic software
package16. The most relevant crystal data for complex are
quoted in Table-1 and the selected bond distances and angles
are listed in Table-2.
Antibacterial assay: The ligand and the complex were
dissolved in sterile water and tested against three reference
strains for antibacterial activity, respectively. The antibacterial
assay was performed using a modified version of the 2-fold
serial dilution method17, in which the concentration of comp-
ounds decreased half as many in a sterile culture medium
containing broth as the nutrient and the strains were incubated
16 h in the culture mediums at the constant temperatures 37 ºC
after being activated and misce bene after being added to the
test tubes of chemical medicine, then readings were taken
after 24 h of incubation at the constant temperatures 37 ºC.
All other test conditions were standardized. The resultant
turbidities in all tubes were estimated visually and the lowest
drug concentrations were found, which is defined minimum
inhibitory concentration (MIC). After 48 h of continuous
incubation, the minimum bacterial concentration (MBC) was
defined, too.
Temperature (K)
V (Å3)
Calculated density (g cm-3)
Crystal size (mm3)
µ (mm-1)
0.49 × 0.46 × 0.40
0.507
Limiting indices
-16 ≤ h ≤ 20, -10 ≤ k ≤ 8,
-23 ≤ l ≤ 23
5190/3866
0.0621, 0.1166
0.0405, 0.0989
0.512, -0.513
Reflections collected / unique
R1, wR2 [all data]
R1, wR2 [I > 2σ(I)]
Largest diff. peak and hole (e Å-3)
TABLE-2
SELECTED BOND LENGTHS (Å) AND
ANGLES (º) FOR Ca(II) COMPLEX
Ca1-O10i
2.322 (2)
2.323 (2)
Na1-O7iii
Na1-O3iv
2.377 (2)
2.403 (2)
2.412 (2)
2.413 (2)
2.447 (2)
2.456 (2)
Ca1-O9
Ca1-O2i
2.339 (2)
2.362 (2)
2.402 (2)
2.435 (2)
162.14 (8)
81.60 (8)
80.91 (8)
92.07 (9)
82.15 (8)
82.73 (8)
88.51 (8)
108.77 (8)
169.79 (8)
95.17 (7)
105.54 (8)
82.97 (8)
106.45 (8)
161.02 (8)
78.57 (7)
Na1-O1
Na1-O4v
Na1-O8vi
Na1-O5
Ca1-O6ii
Ca1-O1
Ca1-O5
O10i-Ca1-O9
O10i-Ca1-O2i
O9-Ca1-O2i
O10i-Ca1-O6ii
O9-Ca1-O6ii
O2i-Ca1-O6ii
O10i-Ca1-O1
O9-Ca1-O1
O2i-Ca1-O1
O6ii-Ca1-O1
O10i-Ca1-O5
O9-Ca1-O5
O2i-Ca1-O5
O6ii-Ca1-O5
O1-Ca1-O5
O7iii-Na1-O3iv 84.60 (9)
O7iii-Na1-O1
O3iv-Na1-O1
O7iii-Na1-O4v
O3iv-Na1-O4v
O1-Na1-O4v
97.56 (8)
165.63 (9)
83.47 (9)
106.60 (9)
87.77 (9)
O7iii-Na1-O8vi 101.33 (9)
O3iv-Na1-O8vi
O1-Na1-O8vi
O4v-Na1-O8vi
O7iii-Na1-O5
O3iv-Na1-O5
O1-Na1-O5
O4v-Na1-O5
O8vi-Na1-O5
81.34 (9)
84.30 (8)
171.20 (10)
163.22 (9)
103.79 (8)
77.97 (7)
80.22 (8)
94.36 (9)
Symmetry codes: (i) -x+1/2, y+1/2, -z+1/2; (ii) -x+1/2, y-1/2, -z+1/2;
(iii) -x, -y+1, -z; (iv) -x, -y, -z; (v) x, y+1, z; (vi) x, y-1, z.
RESULTS AND DISCUSSION
IR spectra: In the infrared spectra, the ν(COOH) vibration
of the free ligand are at 1718 cm-1. For the complex, the vibration
was shifted to 1677 cm-1, which can be explained that the
carboxylate oxygen atoms of 2-(phenylsulfonamido) acetic
acid ligand are involved in the coordination with calcium
atoms as bridging didentate18. The bands of the -SO2-NH-
groups at 3248, 1320 and 1155 cm-1 show that there are uncoor-
dinated atoms of the groups, because compared with the free
ligand the strong absorption bands are not shifted. In addition,
the band at 3423 cm-1 shows that the complex contains water

Vol. 25, No. 4 (2013)
Synthesis and Antibacterial Activity of Ca(II) Complex with 2-(Phenylsulfonamido)acetic Acid 1915
molecules, which are in accordance with the results of
elemental analysis.
Structure description: Perspective view of the molecule
in a unit cell and molecular packing arrangement are shown
in Figs. 2 and 3, respectively. It can be seen that the coordi-
nation environment of the Ca(II) atom consists of three oxygen
atoms from the three 2-(phenylsulfonamido)acetic acid ligands
and three oxygen atoms from the coordinated water molecules,
making up a distorted octahedral environment. The coordination
atoms (O(5), O(6), O(9), O(10)) are situated equatorial place
and the coordination atoms (O(1), O(2)) are situated axial
place. In the complex molecule, the Na(II) atom coordinates
with two oxygen atoms from the two carboxylato group of
two 2-(phenylsulfonamido)acetic acid ligands, one oxygen
atom of S=O group and three oxygen atoms from the coordinated
water molecules, also making up a distorted octahedral environ-
ment. The coordination atoms (O(1), O(3), O(4), O(8)) are
situated equatorial place and the coordination atoms (O(5),
O(7)) are situated axial place. The distances of the Ca(1)-O
bonds are in the range of 2.322(2) 2 - 2.435(2) Å, which are
similar to the Ca-O bond lengths reported previously19.
Fig. 4. Coordination polyhedron of Ca and Na atoms in the complex, and
the 2D infinite net structure of complex viewed down the a axis.
Hydrogen atoms and phenyl groups are omitted for clarity
Antibacterial activity: The antibacterial activity of the
2-(phenylsulfonamido)acetic acid ligand and Ca(II) complex
were assayed using three bacterial strains (Escherichia coli,
Bacillus subtilis and Staphylococcus white). The antibacterial
results of the complex are listed in Table-3 and the results
indicate that the Ca(II) complex shows considerable antibac-
terial activity. Compared with the complex, the N-2-(phenyl-
sulfonamido)acetic acid ligand did not show antibacterial
activity. So the complex will provide potential applications in
the broad spectrum of the antibacterial field.
TABLE-3
Fig. 2. Molecular structure of the complex, where the thermal ellipsoids
were drawn at 30 % possibility. Ca-Na distance is 3.7567(11) Å
MIC AND MBC OF COMPLEX AGAINST
THREE BACTERIAL STRAINS
Strains
MIC (mg/mL)
MBC (mg/mL)
Escherichia coli
Bacillus subtilis
Staphylococcus white
0.675
0.675
0.625
0.675
1.250
0.625
MIC: Minimal inhibitory concentration. MBC: Minimal bactericidal
concentration.
Conclusion
In summary, a novel Ca(II) complex has been synthesized
and structurally characterized. The Ca(II) ion is coordinated
by three oxygen atoms from the three 2-(phenylsulfonamido)
acetic acid ligands and three oxygen atoms from the coordi-
nated water molecules. The antibacterial activity of the Ca(II)
complex indicates that the Ca(II) complex shows considerable
antibacterial activity against Escherichia coli, Bacillus subtilis
and Staphylococcus white.
Fig. 3. One dimensional chain of the complex
ACKNOWLEDGEMENTS
The authors would like to thank the National Natural
Science Foundation of China (No. 21171132 and 20671073),
the Promotive Research Fund for ExcellentYoung and Middle-
aged Scientisits of Shandong Province (2010BSA07004) and
Science Foundation of Weifang University.
The complex forms one dimensional chain structure along
the b axis by intramolecule and intermolecule hydrogen bonds
and π-π stacking. The coordination polyhedron of Ca and Na
atoms in the complex and the 2D infinite net structure of complex
viewed down the a axis is shown in Fig. 4.

1916 Xi-Shi et al.
Asian J. Chem.
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