A 1-D Cd(II) complex based on 2-(1 H -imidazole-1- ylmethyl)-1 H -benzimidazole and 1,3,5- benzenetricarboxylate

Article abstract of DOI:10.1080/15533174.2013.776603

A new complex, {[CdCl(H₂btc^-)(imb)]·H ₂O}_n (1), has been synthesized through the reaction of CdCl₂·2.5H₂O with ligands 2-(1H-imidazole-1- ylmethyl)-1H-benzimidazole (imb) and 1,3,5-benzenetricarboxylic acid (H ₃btc) in water at 80°C. Single-crystal X-ray diffraction analysis shows that complex 1 exhibits 1-D double-stranded chain in which two Cd(II) ions are bridged by two carboxyl groups from two benzenetricarboxylates. These 1-D double-stranded chains are further stacked via hydrogen bonds and the π-π interactions leading to 3-D structure. A thermogravimetric analysis was carried out and the fluorescent property of the complex was investigated. Supplemental materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2013.776603

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A 1-D Cd(II) Complex Based on 2-(1H-imidazole-1-
ylmethyl)-1H-benzimidazole and 1,3,5-
Benzenetricarboxylate
Xiuxiu Wang a , Xiao Han a , Yang Yang a & Xiangru Meng a
a The College of Chemistry and Molecular Engineering , Zhengzhou University , Zhengzhou ,
450001 , P. R. China
Accepted author version posted online: 22 May 2013.
To cite this article: Xiuxiu Wang , Xiao Han , Yang Yang & Xiangru Meng (2013): A 1-D Cd(II) Complex Based on 2-(1H-
imidazole-1-ylmethyl)-1H-benzimidazole and 1,3,5-Benzenetricarboxylate, Synthesis and Reactivity in Inorganic, Metal-
Organic, and Nano-Metal Chemistry, DOI:10.1080/15533174.2013.776603
To link to this article: http://dx.doi.org/10.1080/15533174.2013.776603
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A 1-D Cd(II) Complex Based on 2-(1H-imidazole-1-ylmethyl)-1H-benzimidazole and 1,3,5-
Benzenetricarboxylate
Xiuxiu Wang, Xiao Han, Yang Yang, and Xiangru Meng*
The College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001,
P. R. China
In this paper, a new complex, {[CdCl(H2btc-)(imb)]·H2O}n (1) has been synthesized
through the reaction of CdCl2·2.5H2O with ligands 2-(1H-imidazole-1-ylmethyl)-1H-
benzimidazole (imb) and 1,3,5-benzenetricarboxylic acid (H3btc) in water at 80 oC. Single
X-ray diffraction analysis shows that complex 1 exhibits 1-D double-stranded chain in
which two Cd(II) ions are bridged by two carboxyl groups from two
benzenetricarboxylates. These 1-D double-stranded chains are further stacked via
hydrogen bonds and the π-π interactions leading to 3-D structure. A thermogravimetric
analysis was carried out and the fluorescent property of the complex was investigated.
[Supplementary materials are available for this article. Go to the publisher’s online
edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
ChemistrySynthesis and Reactivity in Inorganic, Metal-Organic for the following free
supplemental resources(s): Figures of the Spectrum Complex].
The authors gratefully acknowledge the financial support by the National Natural Science Foundation of China (Nos.
J1210060).
Address correspondence to Xiangru Meng, The College of Chemistry and Molecular Engineering, Zhengzhou University,
Zhengzhou 450001, P. R. China. E-mail: mxr@zzu.edu.cn
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Key words Cd(II)-complex, crystal structure, fluorescent property, thermogravimetric analysis
INTRODUCTION
Investigation on the design, syntheses, structures and properties of the complexes is becoming
popular due to their potential applications as electronic, optic, magnetic and catalytic materials.[1-
5] However, it is often difficult to control the structures of the final metal-organic assemblies and
to predict the exact nature of the complexes[6,7] owning to the influence of many factors, like
solvent, template, temperature, pH value of the solution, geometric requirements of the metal
ions, counter ions, the nature of the ligands.[8-10] Among the factors mentioned above, the skillful
selection of organic ligands possessing appropriate coordination sites is crucial for designing
novel complexes.[11,12] Multifunctional N-heterocyclic ligands such as imidazole, triazole,
tetrazole, benzimidazole, benzotriazole, pyridine, pyrazine, hexahydropyridine, piperazine and
their derivatives[13-17] possess strong coordinating capability and display diverse conformations
and different coordination modes when coordinate to metal ions. Meanwhile, aromatic
polycarboxylic acids like 1,2-benzenedicarboxylic acid (o-H2bdc), 1,3-benzenedicarboxylic acid
(m-H2bdc), 1,4-benzenedicarboxylic acid (p-H2bdc), 1,3,5-benzenetricarboxylic acid (H3btc),
1,2,4,5-benzenetetracarboxylate (H4btec) and so forth[18-20] can exhibit versatile coordination
modes, for instance monodentate mode, symmetric bidentate mode, asymmetric bidentate mode,
bridging mode, mix-bridging mode.[21-24] In addition, Cd(II) ion is able to coordinate
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simultaneously to both oxygen-containing and nitrogen-containing ligands and the final products
can exhibit promising luminescent properties.[18,25]
Herein, we select 2-(1H-imidazole-1-ylmethyl)-1H-benzimidazole (imb) in which the
methylene group can freely rotate to meet the requirement of coordination geometries of metal
ions in the assembly process and 1,3,5-benzenetricarboxylic acid (H3btc) as ligands to react with
CdCl2·2.5H2O and have obtained complex {[CdCl(H2btc-)(imb)]·H2O}n (1). The results indicate
O atoms from H3btc and N atoms from imb can coordinate to Cd(II) ion simultaneously. The IR
spectrum, the fluorescent property and thermogravimetric feathures have also been investigated.
EXPERIMENTAL SECTION
General Details
The ligand 2-(1H-imidazole-1-ylmethyl)-1H-benzimidazole (imb) was synthesized according to
the literature method.[26,27] All chemicals were of AR Grade from commercial sources and were
used without further purification. IR data were recorded on a BRUKER TENSOR 27
spectrophotometer with KBr pellets in the 400-4000 cm-1 region. Elemental analyses (C, H, and
N) were carried out on a FLASH EA 1112 elemental analyzer. PXRD pattern was recorded using
Cu- Kα radiation on a PANalytical X’Pert PRO diffractometer. TG measurement was performed
by heating the sample from 30 oC to 700 oC at 10 oC min-1 in air on a NETZSCH STA 409
PC/PG differential thermal analyzer. Steady state fluorescence measurements were performed
using a Fluoro Max-P spectrofluorimeter at room temperature in the solid state.
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Synthesis of {[CdCl(H2btc-)(imb)]·H2O}n (1)
A mixture of imb (0.1 mmol), CdCl2·2.5H2O (0.1 mmol), H3btc (0.1 mmol) and water (10 mL)
was sealed into a 25 mL Teflon-lined stainless autoclave and heated at 80 oC for 72h. The
reaction mixture was then allowed to cool to room temperature at rate of 10 oC/h. Colorless
crystal of {[CdCl(H2btc-)(imb)]·H2O}n was collected with a yield of 54% (based on Cd). Anal.
Calcd for C20H17CdClN4O7(573.225): C, 41.90; H, 2.99; N, 9.77%. Found: C, 42.08; H, 3.02; N,
9.53%. IR(KBr, cm–1): 3449(w), 3131(w), 1674(s), 1618(s), 1555(s), 1431(w), 1367(s), 1280(w),
1240(m), 1090(m), 1028(w), 753(s), 726(w), 698(w), 654(w), 619(w).
Single-Crystal Structure Determination
A suitable single crystal of complex 1 was carefully selected and glued to a thin glass fiber.
Crystal structure determinations by X-ray diffraction were performed on a Rigaku Saturn 724
CCD area detector with graphite monochromator for the X-ray source (Mo-Kα radiation, λ =
0.710 73 Å) operating at 50 kV and 40 mA. The data were collected in ω scan mode at
temperature of 293(2) K, and the crystal-to-detector distance was 45 mm. An empirical
absorption correction was applied. The data were corrected for Lorentz-polarization effects. The
structures were solved by direct methods and completed by difference Fourier syntheses and
refined by full-matrix least-squares using the SHELXS-97 program package.[28] All non-
hydrogen atoms were refined anisotropically. The hydrogen atoms of the ligands were positioned
geometrically and refined using a riding model. The hydrogen atoms of the water molecules
were found at reasonable positions in the differential Fourier map and located there. All the
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hydrogen atoms were included in the final refinement. Crystallographic crystal data and structure
processing parameters for complex 1 are summarized in detail in Table 1. Selected bond lengths
and bond angles are listed in Table 2. Hydrogen bonds are given in Table 3.
RESULTS AND DISCUSSION
IR Spectroscopy
As shown in FIG. S1, the IR spectra of complex 1 exhibits that the absorption band at 3449 cm-1
could be associated with the stretching vibrations of O-H. The absorption band at 3131 cm-1
originates from the stretching vibrations of Ar-H. The absorption bands at 1618 cm–1, 1555 cm–1,
1431 cm–1, and 1367 cm–1 originate from the C=C and C=N stretching vibrations. The absorption
band at 753 cm-1 is corresponding to characteristic stretching vibrations of
absorption band at 698 cm–1 can be attributed to the stretching vibrations of
or
. The
. In addition, the
separations (Δ) between νa(COO) and νs(COO) are different for the unidentate, chelating
(bidentate) and bridging complexes. In complex 1, H2btc- group exhibits the νa(COO) and
νs(COO) at 1555 cm–1and 1431 cm–1(Δ = 124 cm–1). This Δ is comparable to those of bridging
complex and H2btc- group can be assigned to bridging mode.[29] Furthermore, the very strong
absorption band observed at 1674 cm–1 can be attributed to the presence of COOH unit. These
analyses are consistent with the results of the X-ray diffraction.
Structural Description
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Single X-ray diffraction analysis reveals complex 1 crystallizes in the triclinic space P-1. All of
the Cd(II) ion is equivalent and five-coordinated. FIG. 1 depicts the coordination environment of
the Cd(II) center. It can be clearly seen that each Cd(II) ion is in a distorted trigonal biyramid
coordination geometry. The apical positions are occupied by one O atom (Cd-O: 2.203(3) and
2.380(4) Å) from the carboxyl of H2btc- group and one terminal Cl atom (Cd-Cl: 2.376(4) Å).
The equatorial plane is completed by two N atoms (Cd-N: 2.246(4) and 2.265(4) Å) from the
benzimidazole ring and imidazole ring of two imb ligands and one O atom from the carboxyl of
H2btc- group. In addition, as shown in FIG. 2, only one carboxyl of each 1,3,5-
benzenetricarboxylate coordinates to the Cd(II) ion and bridges two Cd(II) ions in pairs leading
to a dinuclear structure [Cd2Cl2(H2btc-)2], in which the distance of Cd1···Cd1#1 (Symmetry code
#1: -x+2, -y+2, -z+2) is 4.341 Å. The dimers are further linked to give a 1-D double-stranded
chain through bridging imb ligands (FIG. 3). The intrachain Cd···Cd distance separated by the
ligand imb is 9.398 Å. Furthermore, it is necessary to analyze the conformation of ligand imb
since the flexible can adopt different conformations in the process of obtaining complexes.
Values in the ranges 0-(±)90o can be indicative of cis or syn conformation, while values in the
range (±)90-180o can be indicative of trans or anti conformation.[30-32] In the crystal structure of
complex 1, all of the imb ligands are equivalent and the torsion angle of N1-N2-C4-C5 is -
117.2o. Thus, ligand imb adopts trans conformation in complex 1. Additionally, there are five
kinds of hydrogen bonds in complex 1 (FIG. 4), N-H···O hydrogen bonds between benzimidazole
groups and uncoordinated water molecules, O-H···O hydrogen bonds between carboxyl/carboxyl
groups, and between uncoordinated water molecules and carboxyl groups, O-H···Cl hydrogen
bonds between carboxyl groups and Cl atoms, and between uncoordinated water molecules and
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Cl atoms. Meanwhile, as illustrated in FIG. 3, on the same side of the 1-D chain the separation
between benzene rings from H2btc- groups and benzimidazole rings from imb ligands is 3.35 Å,
so there are π-π interactions. These 1-D double-stranded chains are stacked via hydrogen bonds
and the π-π interactions leading to 3-D structure (FIG. 5).
XRD Pattern and Thermogravimetric Analysis
To confirm the phase purity of these complexes, PXRD pattern was recorded for 1, and it is
comparable to the corresponding simulated one calculated from the single-crystal diffraction data
(FIG. S2 in the Supplementary material), indicating a pure phase of the bulk sample.
Thermogravimetric analysis (TGA) of 1 was performed by heating the complex from 30 oC to
700 oC at 10 oC min-1in air. As shown in FIG. S3 in the Supplementary material, the first mass
loss of 3.23% occurs between 50 oC to 189 oC, corresponding to the release of the crystal water
molecules (Calcd 3.14%). Then the solid continues to lose mass from 295 oC to 555 oC
corresponding to the release of Cl atoms and the decomposition of imb ligands and 1,3,5-
benzenetricarboxylates. Finally, a plateau occurs from 555 oC to 700 oC. The residue equals
22.67%, which is attributed to CdO (Calcd 22.40%).
Fluorescence Spectrum
It is well-known that a number of d10 transition metal complexes exhibit interesting fluorescent
properties. For instance, Cd(II) complexes have been investigated for fluorescent properties and
potential applications as fluorescent materials, such as light-emitting diodes.[33] So the
fluorescent property of complex 1 was determined in the solid state at room temperature. As
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shown in FIG. 6 it exhibits an emission band at about 327 nm when excited at 295 nm. The
fluorescent properties of uncoordinated ligand imb and H3btc were also measured in the solid
state at room temperature to understand the nature of the emission band. The free ligand imb
displays an emission band at 303 nm (λex = 290 nm) and H3btc gives an emission band at 318 nm
(λex = 290 nm), respectively. The result reveals that the emission band of complex 1 may be
involved with contributions from imb ligands and H2btc- groups.[34-36] Compared to the bands for
uncoordinated ligand imb and H3btc, the emission spectrum of complex 1 appears bathochromic
shift.
CONCLUSION
In summary, we have successfully obtained a new complex through reacting 1,3,5-
benzenetricarboxylic acid with Cd(II) ions in the presence of a flexible N-heterocyclic ligand 2-
(1H-imidazole-1-ylmethyl)-1H-benzimidazole (imb) in water. In 1, imb ligands coordinate to
Cd(II) ions with trans conformation and every partially deprotonated 1,3,5-
benzenetricarboxylate bridges two Cd(II) ions. The result illustrates the flexible imb has the
ability to adjust its configuration to meet the coordination requirements of metal centers, and
1,3,5-benzenetricarboxylate could adopt different coordination modes according to the pH values
to connect metal centers. It is predicted that more metal-organic complexes containing neutral
ligands and carboxylate anions with interesting structures as well as physical properties will be
synthesized.
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SUPPLEMENTARY MATERIAL
Crystallographic data reported in this paper have been deposited with the Cambridge
Crystallographic Data Center as supplementary publication. CCD number is 854253. These data
can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving. htm (or from the
Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336033).
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FIG. 1. Coordination environment of the Cd(II) center in complex 1 with the atom numbering
scheme. Uncoordinated water molecules and part of hydrogen atoms are omitted for clarity
(Symmetry code #1: -x+2, -y+2, -z+2; #2: x+1, y, z).
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FIG. 2. View of dinuclear structure in complex 1 connected by carboxyl groups (Symmetry code
#1: -x+2, -y+2, -z+2).
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FIG. 3. View of the 1-D double-stranded chain of complex 1 connected by imb ligands.
Uncoordinated carboxyl of H2btc- groups and uncoordinated water molecules are omitted for
clarity.
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FIG. 4. View of hydrogen bonds in 1.
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FIG. 5. 3-D structure of complex 1 in the solid state supported by hydrogen bonds and π-π
interactions.
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4000
3500
3000
2500
2000
complex 1
H btc

1500
imb
1000
500
0
280
300
320
340
360
380
400
Wavelength(nm)
FIG. 6. Emission spectra of uncoordinated ligand imb, H3btc and complex 1 in the solid state at
room temperature.
Table 1 Crystallographic data and structure processing parameters of complex 1
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
C20H17CdClN4O7 Volume (Å 3)
983.2(3)
2
573.23
293(2)
Z
F(000)
572
Triclinic
P-1
Crystal sizes (mm)
0.23  0.20  0.19
R(int)
0.0194
3841 / 0 / 309
1.024
9.3981(19)
9.835(2)
11.985(2)
98.01(3)
Data/restraints/parameters
Goodness-of-fit on F2
Final Ra indices [I>2σ(I)]
b (Å )
c (Å )
R1 = 0.0439
wR2 =0.1327
α(deg)
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β(deg)
γ(deg)
107.62(3)
106.19(3)
R indices (all data)
R1 = 0.0469
wR2 = 0.1398
Table 2 Selected bond distances (Å) and angles (deg) of complex 1
Cd(1)-O(2)#1
Cd(1)-Cl(1)
Cl(1)-Cd(1)-
O(1)
2.203(3) Cd(1)-N(3)#2
2.376(4) Cd(1)-O(1)
2.246(4) Cd(1)-N(1)
2.265(4)
2.380(4) N(1)-Cd(1)-O(1) 83.99(14)
176.28(11) O(2)#1-Cd(1)- 139.54(14) O(2)#1-Cd(1)-
N(3)#2 N(1)
123.45(15) O(2)#1-Cd(1)- 89.60(14) N(3)#2-Cd(1)-
Cl(1) Cl(1)
94.63(15) O(2)#1-Cd(1)- 93.99(13) N(3)#2-Cd(1)-
O(1) O(1)
96.99(15)
86.58(14)
91.30(13)
N(3)#2-Cd(1)-
N(1)
N(1)-Cd(1)-
Cl(1)
Symmetry transformations used to generate equivalent atoms: #1 -x+2, -y+2, -z+2; #2 x+1, y, z.
Table 3 Hydrogen bonds of complex 1
D-H···A
d(D-H) (Å) d(H···A) (Å) d(D···A) (Å) <(D-
H···A)(deg)
160.5
N(4)-H(4C)···O(7)
O(7)-H(1W)···O(6)
O(3)-H(3)···O(6)#2
O(5)-H(5)···Cl(1)#4
O(7)-H(2W)···Cl(1)#5
0.86
1.97
2.798(6)
2.941(7)
2.526(5)
2.617(5)
3.036(7)
0.73(9)
0.82
2.23(9)
1.75
165(9)
157.2
151.7
177(8)
0.82
1.87
0.78(8)
2.26(8)
Symmetry transformations used to generate equivalent atoms: #2 x+1, y, z; #4 x, y+1, z; #5 -x+1,
-y+2, -z+1.
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