Synthesis, crystal structure, and electrochemical property of the complex [Co(tfbdc)(DMF)2(H2O)2] (tfbdc = Tetrafluoroterephthalate; DMF = N,N-Dimethylformamide)

Article abstract of DOI:10.1080/15533174.2011.609208

One complex [Co(tfbdc)(DMF)₂(H₂O)₂] (tfbdc = tetrafluoroterephthalate) was synthesized by the reaction of tetrafluoroterephthalatic acid with cobalt(II) nitrate hexahydrate in mixture solvent. This complex was characterized by elemental analysis, infrared (IR) spectra, cyclic voltammetry, and x-ray single-crystal structure analysis. This complex crystallizes in the monoclinic system with space group P2(1)/n. The Co(II) ion has a distorted octahedral geometry coordinated by two O atoms from two tetrafluoroterephthalate (tfbdc), two O atoms from two water molecules, and two O atoms from two N,N-dimethyl formamide molecules. Each tfbdc ligand bridges two Co(II) ions in end-to-end fashion, forming a straight chain. These chains are connected by hydrogen bonds, forming a two-dimensional supramolecular network structure. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.609208

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:1299–1304, 2011
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.609208
Synthesis, Crystal Structure, and Electrochemical Property
of the Complex [Co(tfbdc)(DMF)2(H2O)2] (tfbdc =
Tetrafluoroterephthalate; DMF = N,N-Dimethylformamide)
Enjing Zhu,1 Qi Liu,1,2 Lili Yu,1 Mingyang He,1 Qun Chen,1 Zhidong Chen,1
Shengchun Chen,1 and Zhihui Zhang1
1School of Chemistry and Chemical Engineering and Jiangsu Province Key Laboratory of Fine
Petrochemical Technology, Changzhou University, Changzhou, Jiangsu, P. R. China
2State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu, P. R. China
which have flexible –CH2– spacer functions of varying lengths,
benzenedicarboxylic acids have a rigid aromatic unit as the
spacer, which can make them a very special system that
can have interesting electronic and magnetic interactions be-
tween the metal ions in the network through possible con-
jugative interaction.[11,12] In spite of the rich coordination
chemistry exhibited by 1,4-benzenedicarboxylatic acid, 1,3-
benzenedicarboxylatic acid, 1,3,5- benzenetricarboxylatic acid,
Br-benzenedicarboxylatic acid, 1,3-tetrafluoroterephthalatic
acid, and 1,2,4,5-benzenetetracarboxylic acid,[13–24] studies on
tetrafluoroterephthalatic acid (H2tfbdc) are less reported.[25–30]
With the aim of understanding the coordination chemistry of
H2tfbdc, we recently began to study the assembly reactions of
H2tfbdc with metal ions via general solution synthetic meth-
ods.[31] Considering the abundant physical and chemical prop-
erty of cobalt carboxylate complexes,[32] such as magnetic
and catalytic properties, we focused our work on the Co(II)
and H2tfbdc system. In this work, we report synthesis, struc-
tural, spectral, and electrochemical features of one-dimensional
zigzag-type coordination polymers [Co(tfbdc)(DMF)2(H2O)2],
obtained from the assembly reaction of the Co(II) ion and
H2tfbdc in a mixture solvent of dimethylformamide (DMF) and
anhydrous ethanol.
One complex [Co(tfbdc)(DMF)2(H2O)2] (tfbdc = tetrafluo-
roterephthalate) was synthesized by the reaction of tetrafluo-
roterephthalatic acid with cobalt(II) nitrate hexahydrate in mix-
ture solvent. This complex was characterized by elemental analysis,
infrared (IR) spectra, cyclic voltammetry, and x-ray single-crystal
structure analysis. This complex crystallizes in the monoclinic sys-
tem with space group P2(1)/n. The Co(II) ion has a distorted oc-
tahedral geometry coordinated by two O atoms from two tetraflu-
oroterephthalate (tfbdc), two O atoms from two water molecules,
and two O atoms from two N,N-dimethyl formamide molecules.
Each tfbdc ligand bridges two Co(II) ions in end-to-end fashion,
forming a straight chain. These chains are connected by hydro-
gen bonds, forming a two-dimensional supramolecular network
structure.
Keywords cobalt(II), coordination polymer, crystal structure, elec-
trochemical property, tetrafluoroterephthalatic acid
INTRODUCTION
Synthesis and structural characterization of framework ma-
terials involving metal dicarboxylate functions have attracted
considerable attention these days owing to their ability to
form structurally diverse assemblies with interesting network
topologies and material properties that make them very use-
ful candidates for applications relating to sorption, storage,
host–guest, catalytic, magnetic, and optical materials.[1–10]
Compared to malonic, succinic, glutaric, and adipic acids,
EXPERIMENTAL
Material
Tetrafluoroterephthalatic acid (H2tfbdc), cobalt(II) nitrate
hexahydrate, N,N-dimethyl formamide (DMF), and anhydrous
ethanol were of reagent grade without further purification before
use.
Received 17 July 2009; accepted 26 July 2011.
The authors thank the Natural Science Foundation of China (number
20671045), the Natural Science Foundation of State Key Laboratory
of Coordination Chemistry of Nanjing University, and the Foundation
of Jiangsu Province Outstanding Science and Technology Innovation
Team for financial support.
Address correspondence to Qi Liu, College of Chemistry and Chem-
ical Engineering, Changzhou University, Changzhou 213164, P. R.
China. E-mail: liuqi62@163.com
Physical Measurements
Elemental analysis (C, H, N) was performed on a Perkin-
Elmer 2400 Series II element analyzer. Fourier-transform in-
frared (FTIR) spectra were recorded on a Nicolet 460 spec-
trophotometer in the form of KBr pellets.
1299

1300
E. ZHU ET AL.
TABLE 1
Crystal structure parameters of the title complex
Formula
Formula weight
Color
Crystal system
Space group
Scan type
a, nm
C14H18F4CoN2O6
477.23
Purple
Monoclinic
P2(1)/n
ψ-ω
0.53295(14)
1.0246(3)
1.7239(5)
94.207(3)
0.9388(4)
2
Calculated Density (g cm−3
)
1.688
0.999
Mu(Mo Kα) (mm−1
Limiting indices
F(000)
)
h: –6,6; k: –13,13; l: –22,22
486
0.30 × 0.23 × 0.19
2.31 to 27.60
7918
Crystal size (mm)
θ range for data collection (◦)
A total reflections collected
Independent reflections
Observed reflections
b, nm
2157 (Rint = 0.0252)
c, nm
2010
β (◦)
µ(Mo Kα) (mm−1
)
0.071073
1.005
0.0316, 0.0996
0.0334, 0.1014
V (nm3)
Z
Goodness-of-fit on F 2
R1, wR2[I>2σ(I)]
R1, wR2(all data)
Temperature (K)
296(2)
TABLE 2
Selected bond lengths (nm)a and bond angles (◦) of the complex
Co1–O4
Co1–O1
Co1–O3
0.21017 (14)
0.21034 (12)
0.21259 (14)
180.0
91.82 (5)
88.18 (5)
90.10 (6)
93.96 (6)
89.90 (6)
86.04 (6)
180.0
Co1–O4A
Co1–O1A
Co1–O3A
O4–Co1–O1
O4–Co1–O1A
O1A–Co1–O1
O4A–Co1–O3A
O1A–Co1–O3A
O4A–Co1–O3
O1A–Co1–O3
0.21017(14)
0.21034 (12)
0.21259 (14)
88.18 (5)
91.82 (5)
180.000 (1)
89.90 (6)
86.04 (6)
90.10 (6)
93.96 (6)
O4–Co1–O4A
O4A–Co1–O1
O4A–Co1–O1A
O4–Co1–O3A
O3A–Co1–O1
O4–Co1–O3
O1–Co1–O3
O3A–Co1–O3
aSymmetry code: A, –x, –y + 2, –z + 1.
Electrochemical measurements were performed using a
Shanghai Company 440A electrochemical analyzer, with a
three-electrode system consisting of a Pt-piece working elec-
trode, a Pt-wire counterelectrode, and a saturated calomel elec-
trode (SCE) reference electrode. All measurements were carried
out at room temperature with a sweep rate of 100 mV s−1 under
N2, in degassed solvents, using 0.1 M NaC1 aqueous solution as
a supporting electrolyte. The complex concentrations were 5.0
× 10−4 M in aqueous solutions. The half-wave potentials E1/2
were obtained from (Epa + Epc)/2.
Synthesis of [Co(tfbdc)(DMF)2(H2O)2]
A 5-ml anhydrous ethanol solution of Co(NO3)2·6H2O
(0.0239 g, 0.082 mmol) was slowly added to a 3-ml N,N-
dimethylformamide solution that contained H2tfbdc (0.0195 g,
0.082 mmol) to afford a purple solution. Upon slow evapo-
ration of the solvent at room temperature for 3 weeks, purple
block crystals were obtained. Anal.: Calc. for C14H18F4CoN2O6
(477.23): C, 35.23; H, 3.77; N, 5.87%. Found: C, 35.25; H,
3.72; N, 5.83%. IR data (cm−1, KBr pellet): 3511(s), 2989(s),
1658(vs), 1620(vs), 1496 (s), 1468 (s), 1438(vs), 1418(s),
TABLE 3
Hydrogen bond distances and angles in the complex
D-H–Aa
D-H (nm)
H–A (nm)
D–A (nm)
D-H–A (◦)
O4—H4A–O1C
O4—H4A–O3C
O4—H4B–O2A
0.0820
0.0820
0.0820
0.2580
0.2320
0.1850
0.32181(19)
0.3040(2)
0.2650(2)
136.00
147.00
165.00
aSymmetry code: A, –x, –y + 2, –z + 1; C, –x + 1, –y + 1, –z + 1.

TETRAFLUOROTEREPHTHALATE COMPLEX
1301
FIG. 1. The molecular structure of the title complex; atoms are shown as 30% thermal ellipsoids.
1387(vs), 1370(vs), 1247(s), 1115(s), 1066(m), 984(s), 911 (m), RESULTS AND DISCUSSION
850(m), 771(m), 731(vs), 681(s), 650(m), 489(s), 418(m).
Crystal Structure Description of
[Co(tfbdc)(DMF)2(H2O)2]
Figure 1 represents the molecular structure coordination
with atom numbering scheme. As shown in Figure 1, tetrafluo-
roterephthalate (tfbdc) ligands attached to the Co(II) atom adopt
a monodentate coordination mode, which is involved in end-
to-end bridging with the metal center. The other two oxygen
atoms from two water molecules and two oxygen atoms from
two N,N-dimethyl formamide (DMF) molecules are also coor-
dinated to the metal center. The coordination environment of
each cobalt(II) center can be described as a distorted octahedral
geometry. The equatorial position is governed by four oxygen
atoms, two from tfbdc ligands [Co1–O1 = 0.21034(12) nm and
Co1–O1A = 0.21034(12) nm], the other two from two water
molecules [Co1–O4 = 0.21017(14), Co1–O4A = 0.21017(14)
nm]. The apical position is occupied by O3, O3A, from oxygen
atoms of N,N-dimethyl formamide [Co1–O3 = 0.21259(14) and
Co1–O3A = 0.21259(14) nm]. The bond distance of Co–O from
the tfbdc ligand is shorter than that from the DMF molecule, in-
dicating that the strength of the Co(II) ion chelated with tfbdc
is stronger than that of the DMF molecule. Moreover, the bond
X-Ray Crystallography
Single-crystal x-ray diffraction measurement of the title com-
plex was carried out with a Bruker Smart Apex CCD diffrac-
tometer at 296(2) K. Intensities of reflections were measured us-
ing graphite-monochromatized Mo Kα radiation (λ = 0.071073
nm) with the ψ-ω scans mode in the range of 2.31 < θ <
27.60◦. The structures were solved by direct methods using
SHELXS-97[33] computer program and refined by full-matrix
least-squares methods on F2 with the SHELXS-97 program
package. Anisotropic thermal factors were assigned to all the
non-hydrogen atoms. Hydrogen atoms were included in cal-
culated position and refined with isotropic thermal parameters
riding on the parent atoms. Crystallographic data and experi-
mental details for structural analyses are summarized in Table
1, the selected bond lengths (nm) and bond angles (◦) are given
in Table 2, and the hydrogen bonds parameters are presented in
Table 3, respectively.
FIG. 2. One-dimensional straight chain of the title compound.

1302
E. ZHU ET AL.
FIG. 3. The packing of the title compound; dashed lines indicate there are hydrogen bonds between the chains.
angle of O3–Co1–O3A lying in the axial position is 180.0◦,
which indicates that the three atoms are in the same line, and
bond angles of O4–Co1–O4, O1A–Co1–O1 are also 180.0 and
180.0(1)◦, respectively, which indicate O1, O1A, O4, and O4
atoms are on the same plane, but bond distances of Co1–O4,
Co1–O1, Co1–O3 are different, leading to the conclusion that
the Co(II) ion has a distorted octahedral geometry. The distance
between Co1–Co1A is 1.1549 nm. Each tfbdc ligand in equato-
rial plane bridges two Co(II) ions in end-to-end fashion, form-
ing a straight chain, as shown in Figure 2. This one-dimensional
chain is quite similar to that of {[Co(4, 4ꢁ-bipy)(H2O)4]·(α-
furacrylic acid)2·(H2O)}n reported by Yang et al.[34] The for-
mation of hydrogen bonds between chains [O4–H4A- - -O1∗
Thermogravimetric Analysis
The thermogravimetric (TG) measurement of the title com-
plex was determined in the range of 20–800◦C in N2. The weight
loss of 28.17% occurs at a temperature range of about 110 to
240◦C, which is attributed to the volatilization of two DMF
molecules (calcd. 30.59%). The weight loss of 53.38% from
240 to 750◦C corresponds to the elimination of two coordinated
H2O molecules and the pyrolysis of tfbdc ligands. The remain-
ing weight of 16.03% at 750◦C corresponds to the percentage
(15.70%) of final product CoO. Because hydrogen bond ac-
tion exists between hydrogen atoms of the coordinated water
molecules and the oxygen atoms of the tfbdc ligands, losing the
coordinated water molecules is harder than for DMF molecules
under the compound heated.
= 0.32181(19) and 0.3040(2) nm], and O3–H3A- - -O2A
=
0.2650(2) nm], as shown in Figure 3, leads to the production
of a two-dimensional network. The shortest Co(II)- - -Co(II)
distance between the closest neighbors in the same layer via
hydrogen bonds is 0.5329 nm.
Electrochemical Property
The redox behavior of the [Co(tfbdc)(DMF)2(H2O)2] com-
plex was studied by cyclic voltammetry (CV) in aqueous solu-
tion. As shown in Figure 4, during scanning from –1.1 to 1.1
V, the CV diagram of the complex in aqueous solution displays
one pair of anodic and cathodic peaks with peak potentials of
Infrared Spectrum
The IR spectrum of the title complex reflects the binding pat-
terns of water, N,N-dimethyl formamide, and tetrafluorotereph-
thalate moieties. The strong absorption band in the 3600–3000
cm−1 regions corresponds to ν(OH) of the coordination water
molecules in the complex. All carboxylic groups of the organic
ligand in the compound are deprotonated, in agreement with the
IR spectral results, where no absorption peak around 1730 cm−1
for a protonated carboxylic group is observed. The strong peaks
at 1658 cm−1 and at 1468 cm−1, 1438 cm−1 are the νas(OCO) and
νs(OCO) stretching mode of the coordinated tetrafluorotereph-
thalate, while strong absorption at ∼731 cm−1 is the δ (OCO)
bent vibration of tetrafluoroterephthalate. The different values
of 220 cm−1 and 190 cm−1 between νas(OCO) and νs(OCO) in-
dicate that the tetrafluoroterephthalate ligands adopt both mon-
odentate coordination and bridging mode,[35,36] as proved by the
x-ray crystal structure analysis of [Co(tfbdc)(DMF)2(H2O)2].
3
2
1
0
-1
-1.0
-0.5
0.0
0.5
1.0
Potential/V
FIG. 4. Cyclic voltammogram of [Co(tfbdc)(DMF)2(H2O)2] in aqueous solu-
tion, concentration 0.5 mM (scan rate 100 mV s−1).

TETRAFLUOROTEREPHTHALATE COMPLEX
1303
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CONCLUSION
In conclusion, a one-dimensional straight-chain coordination
polymer [Co(tfbdc) (DMF)2(H2O)2] was readily prepared via
reaction of Co(NO3)2·6H2O with ligand of H2tfbdc in the mix-
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SUPPLEMENTARY MATERIAL
CCDC 705175 for [Co(tfbdc)(DMF)2(H2O)2] contains
the supplementary crystallographic data for this pa-
per. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.hmtl [or from the Cam-
bridge Crystallographic Data Center, 12, Union Road, Cam-
bridge CB21EZ, UK; fax (Internet) +44-1223/336-033; e-mail:
deposit@ccdc.cam.ac.uk].
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