Hydrothermal synthesis and crystal structures of three novel Cobalt(II) complexes based on thiabendazole ligand

Article abstract of DOI:10.1080/15533174.2012.749896

Three novel metal-organic complexes, [Co(BDC)(TBZ)] (1), [Co ₂(PDA)₂(H₂O)(TBZ)₂] (2), and [Co(HBTC)(TBZ)(H₂O)] (3) (where BDC = 1,4-benzenedicarboxylate; PDA = 1,4-phenylendi- acetate; TBZ = thiabendazole; BTC = 1,3,5-benzenetricarbox- ylate), have been prepared and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Both 1 and 3 are one-dimensional chain polymers, where two complexes are constructed from multicarboxylates and cobalt atoms. Complex 2 is a two-dimensional network polymer, where two cobalt ions are bridged by an aqua molecule and two carboxylate anions. The 3D structures of the three complexes are stabilized by π-π stacking interactions and hydrogen-bonds. Copyright Taylor and Francis Group, LLC.

Full text of DOI:10.1080/15533174.2012.749896

This article was downloaded by: [University of Edinburgh]
On: 21 June 2013, At: 00:23
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt20
Hydrothermal Synthesis and Crystal Structures
of Three Novel Cobalt(II) Complexes Based on
Thiabendazole Ligand
Shui-Qiang Wei a b , Xian-Hong Yin b , Cui-Wu Lin a , Chun-Juan He b & Hui-Bing Ou b
a College of Chemistry and Chemical Engineering, Guangxi University, Nanning, P. R. China
b College of Chemistry and Chemical Engineering, Guangxi University for Nationalities,
Nanning, P. R. China
Accepted author version posted online: 25 Jan 2013.Published online: 07 Mar 2013.
To cite this article: Shui-Qiang Wei , Xian-Hong Yin , Cui-Wu Lin , Chun-Juan He & Hui-Bing Ou (2013): Hydrothermal Synthesis
and Crystal Structures of Three Novel Cobalt(II) Complexes Based on Thiabendazole Ligand, Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:5, 580-587
To link to this article: http://dx.doi.org/10.1080/15533174.2012.749896
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to
anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should
be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims,
proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in
connection with or arising out of the use of this material.

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:580–587, 2013
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.749896
Hydrothermal Synthesis and Crystal Structures of Three
Novel Cobalt(II) Complexes Based on Thiabendazole Ligand
Shui-Qiang Wei,1,2 Xian-Hong Yin,2 Cui-Wu Lin,1 Chun-Juan He,2
and Hui-Bing Ou2
1College of Chemistry and Chemical Engineering, Guangxi University, Nanning, P. R. China
2College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, P. R.
China
and medicine due to its antiproliferative activities.[19,20] It is an
Three novel metal–organic complexes, [Co(BDC)(TBZ)] (1),
[Co2(PDA)2(H2O)(TBZ)2] (2), and [Co(HBTC)(TBZ)(H2O)] (3)
(where BDC = 1,4-benzenedicarboxylate; PDA = 1,4-phenylendi-
acetate; TBZ = thiabendazole; BTC = 1,3,5-benzenetricarbox-
ylate), have been prepared and characterized by IR spectrum,
elemental analysis, thermogravimetric analysis, and single-crystal
X-ray diffraction. Both 1 and 3 are one-dimensional chain poly-
mers, where two complexes are constructed from multicarboxy-
lates and cobalt atoms. Complex 2 is a two-dimensional network
polymer, where two cobalt ions are bridged by an aqua molecule
and two carboxylate anions. The 3D structures of the three com-
plexes are stabilized by π-π stacking interactions and hydrogen-
bonds.
antimicrobial drug belonging to the benzimidazole derivative,
and has exhibited wide applications in human and veterinary
medicine.[21] The hybrid coordination polymers constructed
by TBZ and aryl-acid combined are rarely reported,[22,23]
although these two ligands are familiar to us. Herein, we report
synthesis, crystal structures, elemental analyses, IR spectrum,
and thermal properties of three novel cobalt(II) complexes
with TBZ, [Co(BDC)(TBZ)] (1), [Co2(PDA)2(H2O)(TBZ)2]
(2), [Co(HBTC)(TBZ)(H2O)] (3), which are formed by π–π
stacking interactions and hydrogen bonds.
EXPERIMENTAL
Keywords cobalt(II)
complex,
single-crystal
structure,
thiabendazole
Materials and Instrumentation
All chemicals were commercial materials of analytical grade
and used without purification. Elemental analysis for C, H,
N, and S was carried out on a Perkin-Elmer 2400 II elemen-
tal analyzer (USA). The FT-IR spectrum was obtained on a
PE Spectrum One FT-IR Spectrometer Fourier transform in-
frared spectroscopy (Perkin-Elmer, USA) in the 4000–400 cm–1
regions, using KBr pellets. Perkin-Elmer Diamond TG/DTA
thermal analyzer (USA) was used to record simultaneous TG
and DTG curves in the static air atmosphere at a heating rate of
10 K min–1 in the temperature range 25–1000◦C using platinum
crucibles.
INTRODUCTION
The crystal engineering and design of solid-state coordi-
nation polymers have become a very attractive field in recent
years.[1–16] As far as we know, selecting appropriate ligands is
the most effective strategy in obtaining coordination polymers.
As bridging ligands, carboxylates, especially multicarboxy-
lates, are of immense interest in the construction of polymeric
coordination architectures because not only the fact that these
polymers have a wide range of structural diversities and poten-
tial applications as porous materials and magnetic materials,
but also the multicarboxylates are capable of functioning
as hydrogen bond donors and/or acceptors.[17] The auxiliary
ligands containing N-donor, such as TBZ, were introduced into
the reaction systems so as to inhibit the expansion of polymeric
frameworks to obtain the desired low dimensional coordination
polymers.[18] TBZ aroused considerable interest in biology
Synthesis of the Complex [Co(BDC)(TBZ)] (1)
A solution of TBZ (0.201 g, 1 mmol) in 3 mL DMF was
added dropwise with stirring at room temperature to a solution
of Co(NO3)2·4H2O (0.3084 g, 1 mmol), H2BDC (0.1660 g,
1 mmol) in the mixture of 10 mL water and 5 mL ethanol. Then
an aqueous solution of sodium hydroxide was added dropwise
with stirring to adjust the pH value of the solution being 6. The
resulting mixture was sealed in a 23 mL Teflon-lined stainless
reactor, kept under autogenous pressure at 130◦C for 72 h, and
then slowly cooled to room temperature at a rate of 5◦C per
hour. The red block crystals suitable for X-ray diffraction were
Received 26 March 2012; accepted 10 November 2012.
Address correspondence to Cui-Wu Lin, College of Chemistry and
Chemical Engineering, Guangxi University, Nanning 530004, P. R.
China. E-mail: cuiwulin@163.com
580

COBALT(II) COMPLEXES BASED ON THIABENDAZOLE LIGAND
581
TABLE 1
Crystallographic data for complexes 1, 2, and 3
1
2
3
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system, space group
a (Å)
C18H11CoN3O4S
424.29
C40H31Co2N6O9S2
921.71
C19H13CoN3O7S
486.30
296(2) K
0.71073 Å
Monoclinic, P2(1)/c
7.3114(18)
20.715(5)
11.181(3)
90
296(2) K
0.71073 Å
Monoclinic, P2/c
11.095(4)
8.592(3)
21.450(6)
90
108.737(14)
90
1936.4(11)
2
296(2) K
0.71073 Å
Monoclinic, P2(1)/c
5.7507(10)
16.135(3)
19.664(3)
90
b (Å)
c (Å)
α (◦)
β (◦)
96.523(4)
90
1682.4(7)
4
1.675
1.176
93.882(2)
90
1820.4(5)
4
1.767
1.110
γ (◦)
Volume (Å3)
Z
Dcalc. (g·cm–3)
1.583
1.030
944
Absorption coefficient (mm–1)
F(000)
860
980
Crystal size (mm)
θ range for data collection (◦)
Reflections collected
Completeness to θ = 25.00
Max. and min. transmission
Data / restraints / parameters
Goodness-of-fit on F2
R indices [I > 2σ(I)]
0.24 × 0.22 × 0.18
0.28 × 0.26 × 0.22
0.21 × 0.18 × 0.12
1.97–25.01
1.94–25.10
1.63–25.10
9040 / 2952 [R(int) = 0.0539] 10110 / 3447 [R(int) = 0.0308] 9845 / 3238 [R(int) = 0.0273]
99.7%
0.8163 and 0.7656
2952 / 0 / 244
1.059
99.7%
0.8051 and 0.7613
3447 / 1 / 267
1.064
R1 = 0.0346
wR2 = 0.0939
R1 = 0.0452
wR2 = 0.1066
0.494 and –0.402
99.9%
0.8783 and 0.8003
3238 / 0 / 280
1.107
R1 = 0.0305
wR2 = 0.0783
R1 = 0.0364
wR2 = 0.0802
0.295 and –0.257
R1 = 0.0438,
wR2 = 0.0998
R1 = 0.0655,
wR2 = 0.1230
0.432 and –0.333
R indices (all data)
Largest diff. features (e Å–3)
isolated directly, washed with ethanol and dried in air (Yield: X-ray diffraction were isolated directly, washed with ethanol,
65%, based on Co). Anal. Calcd. for C18H11CoN3O4S (%): C, and dried in air (Yield: 75%, based on Co). Anal. Calcd. for
50.95; H, 2.61; N, 9.90; S, 7.56. Found: C, 50.98; H, 2.63; N, C40H31Co2N6O9S2 (%): C, 52.12; H, 3.39; N, 9.12; S, 6.96.
9.88; S, 7.55. IR data (KBr pellets, cm–1): 3490 (br), 1653 (s), Found: C, 52.13; H, 3.38; N, 9.11; S, 6.94. IR data (KBr pellets,
1593 (vs), 1553(s), 1495 (m), 1218 (m), 1116 (m), 860 (m), cm–1): 3410 (bs), 1615 (vs), 1485 (s), 1410 (s), 1316 (w), 1087
720 (s), 647(w).
(m), 790 (s), 756 (s), 640 (m).
Synthesis of the Complex [Co2(PDA)2(H2O)(TBZ)2] (2)
TBZ (0.201 g, 1 mmol) and H2PDA (0.1940 g, 1 mmol) were
dissolved in the mixture of 6 mL H2O and 5 mL DMF. Then
an aqueous solution of sodium hydroxide was added dropwise
with stirring to adjust the pH value of the solution being 6. At
last, 10 mL aqueous solution of Co(CH3COO)2·2H2O (0.2665 g,
1 mmol) was input. The resulting mixture was sealed in a 23 mL
Teflon-lined stainless reactor, kept under autogenous pressure
at 130◦C for 72 h, and then slowly cooled to room temperature
at a rate of 5◦C per hour. The red block crystals suitable for
Synthesis of the Complex [Co(HBTC)(TBZ)(H2O)] (3)
The same synthetic procedure as that for 1 was used ex-
cept that H2BDC (0.1660 g, 1 mmol) was replaced by H3BTC
(0.2100 g, 1 mmol). The red block crystals of 3 were obtained
in 45% yield based on Co. Anal. Calcd. for C19H13CoN3O7S
(%): C, 46.92; H, 2.69; N, 8.64; S, 6.59. Found: C, 46.91; H,
2.68; N, 8.65; S, 6.58. IR data (KBr pellets, cm–1): 3600–3200
(br), 1710 (w), 1650 (s), 1608 (vs), 1495(s), 1185 (m), 1096 (m),
895 (m), 815 (s), 660 (s).

582
S.-Q. WEI ET AL.
TABLE 2
The selected bond lengths (Å) and angles (◦) for complexes 1, 2, and 3
Complex 1
Complex 2
Complex 3
2.0769 (16)
Co1-N1
Co1-O4#1
Co1-O1
Co1-N2
Co1-O2
Co1-O3#1
2.078 (3)
2.105 (3)
2.125 (3)
2.142 (3)
2.162 (3)
Co1-O4
Co1-O5
Co1-O3
Co1-N2
Co1-N3
2.040 (2)
2.088 (2)
2.1091 (15)
2.136 (2)
2.181 (3)
2.288 (2)
95.70 (9)
89.00 (7)
93.25 (7)
95.21 (8)
95.52 (8)
169.84 (9)
172.82 (8)
84.64 (9)
98.15 (7)
77.63 (9)
89.86 (8)
173.08 (8)
82.71 (7)
88.05 (8)
90.36 (8)
Co1-O5
Co1-N2
Co1-O6
Co1-O2
Co1-N1
2.1240 (19)
2.1451 (16)
2.1718 (15)
2.1743 (19)
2.1771 (16)
104.90 (7)
90.98 (6)
158.77 (7)
94.89 (6)
95.08 (7)
97.54 (7)
86.92 (7)
77.61 (7)
89.51 (7)
172.68 (7)
153.31 (7)
88.81 (7)
82.64 (6)
60.62 (6)
2.184 (3)
Co1-O1
Co1-O1
N1-Co1-O4#1
O1- Co1-N1
O4#1-Co1-O1
N1- Co1-N2
O4#1- Co1-O1
O1- Co1-N2
N1- Co1-O2
O4#1- Co1-O2
O1-Co1-O2
N2- Co1-O2
O3#1-Co1-N1
O3#1-Co1-O4#1
O3#1-Co1-O1
O3#1-Co1-N2
O3#1-Co1-O2
97.86 (12)
101.14 (11)
153.01 (11)
79.26 (13)
103.91 (12)
98.36 (12)
162.38 (12)
99.60 (11)
61.63 (11)
98.73 (12)
95.03 (12)
61.62 (10)
97.55 (11)
163.86 (11)
91.19 (11)
O4-Co1-O5
O4-Co1-O3
O5-Co1-O3
O4-Co1-N2
O5-Co1-N2
O3-Co1-N2
O4-Co1-N3
O5-Co1-N3
O3-Co1-N3
N3-Co1-N2
O4-Co1-O1
O5-Co1-O1
O3-Co1-O1
N2-Co1-O1
N3-Co1-O1
O5-Co1-N2
O5-Co1-O6
N2-Co1-O6
O5-Co1-O2
N2-Co1-O2
O6-Co1-O2
O5-Co1-N1
N2-Co1-N1
O6-Co1-N1
O2-Co1-N1
O5-Co1-O1
N2-Co1-O1
O6-Co1-O1
O2-Co1-O1
N1-Co1-O1
118.76 (7)
Symmetry codes: #1 x – 1, –y + 3/2, z – 1/2.
Crystal Structure Determination
= 0.71073 Å). Empirical absorption corrections were applied
using the SADABS program.[24] The structure was solved
by the direct method and refined by full-matrix least squares
on F2 using the SHELXTL program.[25] All non-hydrogen
atoms were refined anisotronically. Hydrogen atoms were set
Single crystal of the complex was mounted on glass fiber and
measured on a Bruker SMART CCD area detector (Germany)
at 296 K using graphite monochromated Mo-Kα radiation (λ
TABLE 3
Hydrogen-bond geometry (Å) of complexes
Symmetry
D-H···A
D-H H···A D···A D-H···A
codes
Complex 1
N3-H3··· O4 0.86 2.23 2.880 (4) 132.3 –x + 2, –y +
1, –z
Complex 2
N1-H1···O1 0.86 2.01 2.803 (3) 153.3 –x + 1, –y +
1, –z + 2
O3-H3D···O2 0.85 1.75 2.552 (3) 173.0 –x + 1, y, –z
+ 3/2
Complex 3
N3-H3···O7 0.86 1.97 2.804 (3) 164.2 –x + 1, y –
1/2, –z +
1/2
O6-H6C···O7 0.85 1.82 2.665 (2) 169.9
O6-H6D···O2 0.85 2.06 2.905 (2) 170.3 x + 1, y, z
O4-H4D···O3 0.85 1.80 2.647 (2) 179.9 –x – 1, –y +
1, –z + 1
FIG. 1. The coordination environment of Co(II) ion of the complex 1. All the
hydrogen atoms are omitted for clarity (color figure available online).

COBALT(II) COMPLEXES BASED ON THIABENDAZOLE LIGAND
583
FIG. 4. The coordination environment of Co(II) ion of the complex 2. All the
hydrogen atoms are omitted for clarity (color figure available online).
FIG. 2. The 1D chain and the π-π stacking interactions of complex 1. Unnec-
essary atoms are omitted for clarity (color figure available online).
RESULTS AND DISCUSSION
Description of the Structure
The crystallographic analysis reveals that complexes 1 and
3 belong to the monoclinic system with space group P21/c,
complex 2 crystallizes in the monoclinic P2/c.
The structure of the compound 1 is formed by infinite
one-dimensional chains. The simplest coordination pattern is
in calculated positions and refined by a riding mode, with a
common thermal parameter. The crystal data and structure
refinement details for three complexes are shown in Table 1.
Selected bond lengths and angles of the complexes are listed
in Table 2, and possible hydrogen bond geometries are given in
Table 3.
FIG. 5. The H-bonding and π-π stacking interactions of complex 2 (where
the green dashed lines are H-bonding, the black dashed lines are π-π stacking
interactions). Unnecessary atoms are omitted for clarity (color figure available
online).
FIG. 3. The 2D skeleton of complex 2. Unnecessary atoms are omitted for
clarity (color figure available online).

584
S.-Q. WEI ET AL.
observed in compound 1, where each cobalt atom has an oc-
tahedral environment formed by three chelating bidentate lig-
ands: two nitrogen atoms (N1, N2) from TBZ and four O atoms
(O1, O2, O3, O4) from two BDC ligands (Figure 1). The Co-O
bond lengths vary from 2.105(3) to 2.184(3) Å (see Table 2),
which reveals that the coordination ability of the four O atoms
from the different carboxylates is corresponding. In the over-
all structure of 1, units of [Co(TBZ)]2+ are connected by the
bridging BDC ligands to generate a zigzag chain (Figure 2).
The 1D chains are linked by weak N3–H3A· · ·O4# (symmetry
code #: –x + 2, –y + 1, –z) hydrogen bonds with the distance
of 2.880(4) Å to yield a layered network. Figure 2 also re-
veals that the π-π stacking interactions are formed between the
adjacent TBZ ligands of which the intercentroid distance being
3.7164 and 3.7133 Å. Such contacts link the 2D layers into a 3D
structure.
The X-ray structure shows that complex 2 adopts a two-
dimensional network polymer. The 2D skeleton is formed by
cobalt ions as nodes and PDA dianions as spacers, through
coordination bonds (Figure 3). The CoII central atoms, which
have octahedral coordination, are bridged by two O atoms (O1,
FIG. 6. The coordination environment of Co(II) ion of the complex 3. All the
hydrogen atoms are omitted for clarity (color figure available online).
FIG. 7. A perspective view of H-bonding of complex 3. Unnecessary atoms are omitted for clarity (color figure available online).

COBALT(II) COMPLEXES BASED ON THIABENDAZOLE LIGAND
585
O5) from different PDA ligands, a water molecule (O3), and
two nitrogen atoms (N2, N3) from TBZ (Figure 4). The ni-
trogen atoms are bound with the central atoms in trans po-
sitions to the bridging PDA ligands and water molecule. In
complex 2, two cobalt ions are bridged by an aqua molecule
and two carboxylate anions. Moreover, 2 is further stabilized
by two intramolecular hydrogen bonds between the hydrogens
of the bridging aqua and the oxygens of the terminal mon-
odentate PDA and by weak N-H···O hydrogen bonds from N-H
of TBZ together with carboxylic O atom of PDA (shown in
Figure 5). The crystal structure of compound 2 is also stabilized
by π-π stacking of TBZ ligands with the centroid-centroid
distances of 3.6473 and 3.8107 Å. The 3D structure of com-
plex 2 is stabilized by π-π stacking interactions and hydrogen
bonds.
A perspective view of the molecular structure of the complex
3 along with the atom-numbering scheme is depicted in Figure 6.
The environment of cobalt atoms is modified by incorporation
of a coordinating water molecule (O6) into a trans position
to one of the nitrogen atoms (N2), resulting in change of a co-
ordination mode of one of the BTC ligands from chelating to
monodentate. BTC ligands exhibit three types of coordination
modes: one is uncoordinated, one displays a chelating mode, and
the third adopts a bridging monodentate arrangement, respec-
tively. The central cobalt(II) ion lies in a octahedral coordination
environment with three oxygen atoms (O1, O2, O5) from two
different BTC ligands, a water molecule (O6), and two nitrogen
FIG. 8. A perspective view of the π-π stacking interactions of complex 3
(where the black dashed lines are H-bonding, the red dashed lines are π-π
stacking interactions). Unnecessary atoms are omitted for clarity (color figure
available online).
FIG. 9. The comparison of the coordination modes of the multicarboxylates in three complexes (color figure available online).

586
S.-Q. WEI ET AL.
atoms (N1, N2) from a chelating TBZ ligand. The chains are
connected through N3-H3···O7, O6-H6C···O7 hydrogen bonds
(Table 3) to generate 2D network (Figure 7). The O4-H4D···O3,
O6-H6C···O7, and O6-H6D···O2 hydrogen bonds link the 2D
network into a supramolecular architecture. In addition, TBZ
ligands locate at both side of the molecule and there are π-π
stacking interactions between them of adjacent chains with the
centroid-centroid distances of 3.6816 and 3.5010 Å, as shown
in Figure 8. These interactions are extremely strong and make
the complex be a 3D architecture.
As shown in Figure 9, the TBZ acts as a typical chelating
ligand coordinated to the metal center in all complexes, while the
multicarboxylates from three complexes exhibit different types
of coordination modes. 1 is chelating, 2 displays monodentate
coordination and bridging bidentate mode, while 3 exhibits three
types of coordination modes: one is uncoordinated, one displays
a chelating mode, and the third adopts a bridging monodentate
arrangement.
Thermal Analysis
TG curve of the complex 1 is presented in Figure 10, where
two weight loss steps exist and the decomposition mainly takes
place at 365 and 428◦C. The first weight loss stage may be
related to the removal of BDC (found 37.4%, calcd. 38.6%),
and the second corresponds to the release of TBZ (found
41.2%, calcd. 47.3%). Above 785◦C, nearly no weight loss is
observed.
The thermal decomposition behaviors of complex 2 exhibit
three decomposition stages (Figure 10). The complex loses co-
ordinated water molecules at 162◦C, the weight loss found of
4.5% (calcd. 2.0%). The anhydrous complex loses 40.5% of total
weight in the 313–475◦C temperature range, corresponding to
the removal of a PDA ligand (calcd. 41.6%). When the tempera-
ture holds on rising, the products lose 38.7% of the total weight
in the temperature range of 480–810◦C, which is related to the
loss of TBZ (calcd. 43.6%). The residual percentage weight
at the end of the decomposition of the complex is observed
21.4%.
TG of complex 3 (Figure 10) indicates that 3 loses 3.5% of
total weight from 174 to 203◦C, corresponding to the removal
of the coordinated water molecules. Good agreement between
experimental and calculated values was observed for the weight
loss (calcd. 3.7%). The products lose 43.2% of the total weight
from 240 to 470◦C, which is related to the endothermic decom-
position of BTC (calcd. 42.7%). Upon temperature increase,
the TBZ decomposes gradually, a series of complicated and
consecutive weight losses occur.
CONCLUSION
In this work, we report the synthesis and characterization
of complex [Co(BDC)(TBZ)], [Co2(PDA)2(H2O)(TBZ)2], and
[Co(HBTC)(TBZ)(H2O)] by spectral method (IR), elemental
analysis, thermal analysis, and single-crystal X-ray diffraction
techniques. The previous results show that the configuration of
FIG. 10. The TG curves of complexes 1 (A), 2 (B), and 3 (C).

COBALT(II) COMPLEXES BASED ON THIABENDAZOLE LIGAND
587
ligand plays an important role in affecting the final structure 10. Fang, Q.-R.; Zhu, G.-S.; Xue, M.; Sun, J.-Y.; Wei, Y.; Qiu, S.-L.; Xu,
R.-R. A metal-organic framework with the zeolite MTN topology con-
of the coordination polymers. The successful preparation of the
complexes manifest that the conformations and functions of π-π
stacking interactions and hydrogen bonds are important factors
in influencing the architecture of metal-TBZ complexes.
taining large cages of volume 2.5nm3. Angew. Chem. Int. Ed. 2005, 44,
3845–3848.
11. Benmansour, S.; Setifi, F.; Go`mez-Garc`ıa, C. G. Linkage isomerism in
coordination polymers. Inorg. Chem. 2012, 51, 2359–2365.
12. Biradha, K.; Ramanan, A.; Vittal, J. J. Coordination polymers versus metal-
organic frameworks. Cryst. Growth Des. 2009, 9, 2969–2970.
13. Jing, X. M.; Meng, H.; Li, G. H.; Yu, Y.; Huo, Q. S.; Eddaoudi, M.;
Liu, Y. L. Construction of three metal-organic frameworks based on multi-
functional T-shaped tripodal ligands, H3pyimdc. Cryst. Growth Des. 2010,
10, 3489–3495.
14. Wei, S.-Q.; Lin, C.-W.; Yin, X.-H. Hydrothermal synthesis, crystal structure
of four novel complexes based on thiabendazole ligand. Bull. Korean Chem.
Soc. 2012, 33, 2917–2924.
15. Zhang, Z.; Liu, J.-Z.; Gao, P. Synthesis, crystal structure and thermal prop-
erty of a novel Mn(ꢀ) coordination polymer bridged by imazapyr. J. Chem.
Crystallogr. 2011, 41, 1839–1843.
16. Tong, L.; Wang, Y.; Duan, L. Water oxidation catalysis: influence of anionic
ligands upon the redox properties and catalytic performance of mononuclear
ruthenium complexes. Inorg. Chem. 2012, 51, 3388–3398.
17. Ye, B.-H.; Tong, M.-L.; Chen, X.-M. Metal-organic molecular architectures
with 2, 2’-bipyridyl-like and carboxylate ligands. Coord. Chem. Rew. 2005,
249, 545–565.
18. Xu, Y.-Q.; Zhou, Y.-F.; Yuan, D.-Q.; Hong, M.-C. Blue luminescent zinc(II)-
and cadmium(II)-1,4-phenylenediacetate complexes. Chin. J. Struct. Chem.
2006, 25, 1161–1166.
19. Devereux, M.; McCann, M.; Shea, D. O.; Kelly, R.; Egan, D.; Dee-
gan, C.; McKee, V. J. Synthesis, antimicrobial activity and chemother-
apeutic potential of inorganic derivatives of 2-(4ꢁ-thiazolyl)benzimidazole
{thiabendazole}: X-ray crystal structures of [Cu(TBZH)2Cl]Cl·H2O·EtOH
and TBZH2NO3. Inorg. Biochem. 2004, 98, 1023–1031.
SUPPLEMENTARY MATERIALS
Supplementary material has been deposited with the
Cambridge Crystallographic Data Center (no1. 868779, no2.
868778, no3. 868777; deposit@ccdc.cam.ac.uk or http://www.
ccdc.cam.ac.uk).
REFERENCES
1. Lin, X.; Wang, Y.-Q.; Cao, R.; Li, F.; Bi, W.-H. A new chain-like cad-
mium(II) coordination polymer containing chains of water molecules. Acta.
Crystallogr. C 2005, 61, m292–m294.
2. Cingolani, A.; Galli, S.; Masciocchi, N.; Pandolfo, L.; Pettinari, C.; Siroin,
A. Sorption-desorption behavior of bispyrazolato-copper(II) 1D coordina-
tion polymer. J. Am. Chem. Soc. 2005, 127, 6144–6145.
3. Manna, S. C.; Zangrando, E.; Drew, M. G. B.; Ribas, J.; Chaudhuri,
N. R. Syntheses, crystal structures and magnetic properties of carboxylato-
bridged polymeric networks of Mn(II). Eur. J. Inorg. Chem. 2006, 2,
481–490.
4. Singh, W. M.; Baruah, J. B. Structural study of few p-phenylenediacetate
complexes of Mn2+, Cu2+, Zn2+ and Cd2+. Inorg. Chim. Acta 2009, 362,
4268–4271.
5. Zhou, J.; Sun, C.-Y.; Jin, L.-P. Metal-dependent assembly and structure of
metal 1, 4-phenylenediacetate complexes with 1,10-phenanthroline. J. Mol.
Struct. 2007, 832, 55–62.
6. Eberhardt, R.; Allmendiger, M.; Zintl, M.; Troll, C.; Luinstra, G. A.; Rieger,
B. New zinc dicarboxylate catalysts for the CO2/propylene oxide copoly-
merization reaction: activity enhancement through Zn(II)-ethylsulfinate ini-
tiating groups. Macromol. Chem. Phys. 2004, 205, 42–47.
7. Mori, W.; Sato, T.; Ohmura, T.; Kato, C. N.; Takei, T. Functional microp-
orous materials of metal carboxylate: Gas-occlusion properties and catalytic
activities. J. Solid. State. Chem. 2005, 178, 2555–2573.
8. Supriya, S.; Manikumari, S.; Raghavaiah, P.; Das, S. K. A cyclic
supramolecular (H2O)4 cluster in an unusual Fe3 complex that aggregates
to {Fe3}n with a zig-zag chainlike structure. New. J. Chem. 2003, 27,
218–220.
20. . James, D. M.; Gilles, H. M. (editors) Human Antiparasitic Drugs: Phar-
macology and Usage; Wiley, New York, 1996.
21. Kaniskan, N.; Ogretir, C. Investigation of acid–base behaviour of some
2-pyridylbenzimidazoles using semi-empirical methods. J. Mol. Struct.
2002, 584, 45–52.
22. Wang, Jia-Jun, LV, Ming, SUN, Ya-Ming, CUI, Yun-Cheng. Crystal struc-
ture of a Cu(II) coordination polymer: [Cu(IP)(TBZH)]2n. Chin. J. Struct.
Chem. 2009, ;28, 434–438.
23. Wang, J.-J.; Cui, Y.-C.; Liu, L.-H.; Huang, Y.-J. Crystal structure of a
Mn(II) coordination polymer: [Mn(TP)(TBZH)]2n. Chin. J. Struct. Chem.
2010, 29, 240–244.
9. Dybtsev, D. N.; Chun, H.; Yoon, S. H.; Kim, D.; Kim, K. Microporous man-
ganese formate: a simple metal-organic porous material with high frame-
work stability and highly selective gas sorption properties. J. Am. Chem.
Soc. 2004, 126, 32–33.
24. Blessing, R. H. An empirical correction for absorption anisotropy. Acta.
Crystallogr. A 1995, 51, 33–38.
25. Sheldrick, G. M. SHELXTL97: Program for Refining Crystal Structure
Refinement; University of Go¨ttingen, Germany, 1997.