Crystal structures and electrochemical property of two novel complexes [Cu(o-phth)(H2O)]n and [Co(3-nitro-phth)(4,4′-bipy) 2(H2O)3]n

Article abstract of DOI:10.1080/15533170500225219

A copper(II) complex with o-phthalate acid [Cu(o-phth)-(H ₂O)]_n (1) and a cobalt(II) complex with 3-nitro-phthalic acid and 4,4′-bipyridine [Co(3-nitro-phth) (4,4′-bipy) ₂(H₂O)₃]_n (2) have been synthesized. These two novel complexes were characterized by IR, X-ray crystallography diffraction. Complex 1 belongs to monoclinic crystal with C2 (1)/c space group, the complex 2 triclinic crystal with P-1. Also, electrochemical properties of these complexes and thermal decomposition process of complex 1 were investigated. Copyright

Full text of DOI:10.1080/15533170500225219

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Crystal Structures and Electrochemical Property
of Two Novel Complexes [Cu(o‐phth)(H2O)]n and
[Co(3‐nitro‐phth)(4,4′‐bipy)2(H2O)3]n
Hai‐bin Qiao a , Xiao‐qing Shen a , Hong‐yun Zhang a , Li‐jie Yuan a , Pei‐kun Chen a ,
Hong‐yan Mao a & Hong‐wei Hou a
a Department of Chemistry , Zhengzhou University , Henan, China
Published online: 18 Aug 2006.
To cite this article: Hai‐bin Qiao , Xiao‐qing Shen , Hong‐yun Zhang , Li‐jie Yuan , Pei‐kun Chen , Hong‐yan Mao & Hong‐wei
Hou (2005) Crystal Structures and Electrochemical Property of Two Novel Complexes [Cu(o‐phth)(H2O)]n and [Co(3‐nitro‐phth)
(4,4′‐bipy)2(H2O)3]n , Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 35:8, 627-632, DOI:
10.1080/15533170500225219
To link to this article: http://dx.doi.org/10.1080/15533170500225219
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Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 35:627–632, 2005
Copyright # 2005 Taylor & Francis, Inc.
ISSN: 0094-5714 print/1532-2440 online
DOI: 10.1080/15533170500225219
Crystal Structures and Electrochemical Property of Two
Novel Complexes [Cu(o-phth)(H2O)]n and
[Co(3-nitro-phth)(4,40-bipy)2(H2O)3]n
Hai-bin Qiao, Xiao-qing Shen, Hong-yun Zhang, Li-jie Yuan, Pei-kun Chen,
Hong-yan Mao, and Hong-wei Hou
Department of Chemistry, Zhengzhou University, Henan, China
carboxylate-bridging modes) (Moghimi et al., 2002; Liu et al.,
A copper(II) complex with o-phthalate acid [Cu(o-phth)- 2004). In the interest of studying coordination ability and con-
(H2O)]n (1) and a cobalt(II) complex with 3-nitro-phthalic acid
and 4,40-bipyridine [Co(3-nitro-phth) (4,40-bipy)2(H2O)3]n (2)
have been synthesized. These two novel complexes were charac-
figuration of carboxylate–oxygen with transition metals, a
copper(II) complex with o-phthalate [Cu(o-phth)(H2O)]n and
a cobalt(II) complex with both 3-nitro-phthalic acid and 4,40-
terized by IR, X-ray crystallography diffraction. Complex 1
belongs to monoclinic crystal with C2 (1)/c space group, the
bipyridine [Co(3-nitro-phth)-(4,40-bipy)2(H2O)3]n were syn-
complex 2 triclinic crystal with P-1. Also, electrochemical proper- thesized. The crystal structures and electrochemical properties
ties of these complexes and thermal decomposition process of
complex 1 were investigated.
of these two complexes are discussed.
Keywords 4,40-bipy, o-phthalate, Co(II), Cu(II), hydrogen bond
RESULTS AND DISCUSSION
The crystal data and structural determination summary for
complexes 1, 2 are shown in Table 1. Their selected bond dis-
tances and bond angles are listed Tables 2 and 3 respectively.
INTRODUCTION
In 1994, Constable introduced the term metallo-
supramolecular chemistry to describe the use of odd combi-
nations of metal ions and polydentate organic ligands for the
controlled assembly of large molecular structures held
together by metal-ligand interactions (Christopher, 2000;
Crystal Structure of Complex 1
Two copper atoms are all four coordination in crystal unit,
but have different coordination environments (Figure 1). Four
oxygen atoms from four o-phthalate groups coordinate to the
Cu (1) center and build a nearly square geometry, which is
shown in such angle data: O(4A)–Cu(1b)–O(4G) ¼ 85.7
(2)8, O(4A)–Cu(1B)–O(1B) ¼ 92.04 (17)8, O(4A)–Cu(1B)–
O(1H) ¼ 170.25 (17)8. The values of the copper-oxygen bond
´
Ruiz–Perez and Sanchiz, 2000; Liu et al., 2004). The construc-
tion of metal supramolecular structures with interesting proper-
ties in catalysis, electrical conductivities and molecular-based
magnets have attracted considerable attention in recent
˚
lengths differ from each other [1.939 A for Cu(1B)–O(4A)
˚
and Cu(1B)–O(4G), 1.949 A for Cu(1B)–O(1B) and Cu(1B)–
´
´
years (Ruiz-Perez and Hernandez, 2000a, 2000b; Wei and
Zhang, 1996). Organic carboxylate compounds were excellent
bridging ligands due to their strong coordinative capacity
(bidentate through two carboxylate–oxygen and different
O(1H)]. The angle deviation of Cu(1) from the plane is
0.12588. Two water molecules and two oxygen atoms from
two o-phthalates, each of which supplies one carboxylate–
oxygen, bond with Cu(2B) and form parallelogram geometry.
˚
The bond angle data include: Cu(2B)2O(5E) ¼ 1.950 (5) A,
˚
Cu(2B)2O(2K) #3 ¼ 1.963 (4) A and O(5E)–Cu(2B)–
Received 28 March 2005; accepted 1 June 2005.
This work was supported by the Natural Science Foundation of
China (202710246), the Natural Science Foundation of Henan
Education Department (2004150004) and the Natural Foundation of
Henan Province (02110203).
Address correspondence to Hong-yun Zhang, Department of
Chemistry, Zhengzhou University, Henan 450052, China. E-mail:
wzhy917@zzu.edu.cn
O(2H) ¼ 89.9 (2)8, O(5B)2Cu(2B)2O(2H) ¼ 90.1 (2)8.
Two adjacent benzene ring planes of C(2K), C(3K), C(4K),
C(5K), C(6K), C(7K) and C(2H), C(3H), C(4H), C(5H),
C(6H), C(7H) are parallel, the distance between two planes is
˚
3.47 A, which shows strong p–p interaction existing in
stacking crystals with the other benzene ring at an angle of 31.48.
627

628
H.-B. QIAO ET AL.
TABLE 1
Crystallographic data and structure refinement for complexes 1, 2
Complex 1
Complex 2
Formula
Crystal system
Space group
C32H24Cu4O20
Monoclinic
C28H25CoN5O9
Triclinic
P-1
C2 (1)/c
26.143 (5)
˚
a/A
7.4264 (2)
11.224 (2)
12.836 (3)
79.89 (3)
70.76 (3)
86.07 (3)
1403.2 (5)
1.502
˚
b/A
6.6868 (13)
9.823 (2)
˚
c/A
a/8
b/8
g/8
90
94.11
90
1712.7 (6)
1.905
3
˚
V/A
Dc/Mg m23
Z
2
2.540
2
1.443
m/mm21
Reflens collected
Data/restraints
Ra
2543/1444[R(int) ¼ 0.1305]
1444/0/138
0.0796
5066/5066[R(int) ¼ 0.0000]
5066/0/413
0.0447
Rwb
0.1992
1.032
0.794 and 21.109
0.1062
1.075
0.588 and 20.530
Goodness of fit on F2
23
˚
Drmin and Drmax/e A
Hydrogen bond is exhibited in the crystal structure, with two and two water molecules, in the equatorial plane, while the
hydrogen atoms in coordinating water, bond to carboxylate other nitrogen atom of other 4,40-dipyridyl and one water
oxygen. The crystal structure is stabilized by weak hydrogen molecular oxygen occupy the two axial sites of the octahedron.
˚
bond interactions and strong p–p interactions (Figure 2). Four Co–O bonds with approximate lengths of 2.10 A are
Eight Cus constitute a parallelogram unit, Cu(1A)– shorter than the other two Co–N bonds with lengths of
˚
˚
˚
Cu(1D) ¼ 20.061 A, Cu(1A)–Cu(1E) ¼ 11.942 A, Cu(1D)– 2.150 A. The equatorial plane including Co(1A), O(8A),
Cu(1A)–Cu(1E) ¼ 24.288, as shown in Figure 4.
O(4A), O(9A) and N(2A) is a distorted square plane, as
shown in Figure 3. The axial plane is approximately vertical
to it (at an angle 91.68). The angle: O(7A)–Co(1A)–
N(4A) ¼ 172.088, which shows the octahedron being asym-
metric. In 4,40-bipyridyl, two pyridine cycles are distorted with
Crystal Structure of Complex 2
The cobalt ion has a coordination geometry that approxi-
mates an octahedron. Each Co(II) coordinated by one nitrogen
atom from 4,40-bipyridyl, one oxygen of 3-nitro-phthalic acid
˚
18.6 A, which is less space resistance. With this distortion, the
TABLE 2
˚
Selected bond distances (A) and angles (deg) for complex 1
Cu(1B)–O(4A)
1.939 (4)
Cu(1B)–O(4G)
1.939 (4)
Cu(1B)–O(1B)
Cu(2B)–O(5B)
Cu(2B)–O(2H)
1.949 (4)
1.950 (5)
1.963 (4)
123.7 (6)
92.04 (17)
170.25 (17)
161.38 (7)
85.7 (2)
Cu(1B)–O(1H)
O(1H)–C(1H)
O(3H)–C(8H)
1.949 (4)
1.267 (7)
1.235 (7)
131.2 (4)
89.9 (2)
C(2K)–C(7K)–C(8K)
O(4A)–Cu(1B)–O(1B)
O(4A)–Cu(1B)–O(1H)
O(4G)–Cu(1B)–O(1B)
O(4G)–Cu(1B)–O(4A)
C(1H)–O(1H)–Cu(1H)
O(5E)–Cu(2B)–O(2H)
O(5B)–Cu(2B)–O(2K)
O(2K)–Cu(2B)–O(2H)
O(1H)–Cu(1B)–O(1B)
89.9 (2)
180.00 (15)
91.7 (3)
Symmetry transformations used to generate equivalent atoms: #1 2x þ 1, y 2 1, 2z þ 1/2; #2 x, y 2 1, z;
#3 2x þ 1, y, 2z þ 1/2; #4 2x þ 1, 2y þ 1, 2z þ 1; #5 x, 2y þ 1, z þ 1/2; #6 x, y þ 1, z.

STRUCTURES AND PROPERTY OF TWO NOVEL COMPLEXES
629
TABLE 3
˚
Selected bond distances (A) and angles (deg) for complex 2
Co(1A)–O(8A)
2.094 (2)
Co(1A)–N(2A)
2.148 (2)
Co(1A)–O(7A)
Co(1A)–O(4A)
2.105 (2)
2.099 (2)
83.70 (9)
91.14 (10)
85.89 (10)
168.09 (9)
88.97 (9)
116.4 (3)
116.6 (3)
121.51 (19)
Co(1A)–N(4A)
O(1A)–C(7A)
2.150 (2)
1.234 (4)
97.80 (10)
98.75 (9)
87.19 (9)
89.27 (9)
93.08 (9)
122.06 (19)
122.0 (2)
116.3 (4)
O(8A)–Co(1A)–O(4A)
O(7A)–Co(1A)–O(9A)
O(7A)–Co(1A)–N(2A)
O(4A)–Co(1A)–O(9A)
O(8A)–Co(1A)–O(7A)
C(23A)–N(4A)–C(19A)
C(4A)–C(3A)–N(1A)
C(19A)–N(4A)–Co(1A)
O(8A)–Co(1A)–O(7A)
O(4A)–Co(1A)–N(2A)
N(2A)–Co(1A)–N(4A)
O(8A)–Co(1A)–N(4A)
O(9A)–Co(1A)–N(4A)
C(23A)–N(4A)–Co(1A)
C(9A)–N(2A)–Co(1A)
C(28A)–N(5A)–C(24A)
Symmetry transformations used to generate equivalent atoms: #1 2x þ 2, 2y þ 1, 2z þ 1; #2 2x þ 1,
2y þ 3, 2z þ 1.
4,40-dipyridyl forms a dibridge framework (Figure 4). The IR Spectra
selected bond distances and angles are shown in Table 3.
There are strong O–H ꢀ ꢀ ꢀ O and O–H ꢀ ꢀ ꢀ N hydrogen bonds
in the crystal structure. O(7A)–H(7E) ꢀ ꢀ ꢀ O(5A) in the crystal
structure shows a 4,40-dipyridyl coordinating to a water
molecule weakly by a hydrogen bond (Figure 5). The bond
lengths and angles are shown in Table 4. The structure of Co
framework in complex 2, shown in Figure 6, adopts a chair
conformation (Bhubon Singh et al., 2001).
In the IR spectra of complex 1, a strong and broad band
(O–H stretching vibration) in the 3500–3000 cm21 region
indicates the presence of coordinated water molecule; the
medium intensity peaks at 1564, 1537 and 1488 cm21 are
consistent with the existence of a benzene cycle. The other
strong peaks at 1618 and 1538 cm21, and 1413 and
1366 cm21 can be attributed to yas COO, ys COO, respectively.
In the IR spectra of complex 2, the presence of H2O accounts
FIG. 1. The crystal structural unit of complex 1.

630
H.-B. QIAO ET AL.
FIG. 4. The crystal cell structure of complex 2.
Thermal Analysis
Thermogravimetric analysis of complex 1 reveals that a
weak endothermal peak appears at 149.6 8C. The whole
weight loss is about 6.8% (calculated 7.3%), which suggests
loss of one water molecule. A strong exothermal peak
appears from 212 8C to 432 8C with weight loss of 62%, corres-
ponding to o-phthalate decomposition (calculated 65%), the
residue is 25.2% corresponding to CuO and organic remains.
FIG. 2. The crystal cell structure of complex 1.
for the strong and broad band (O–H stretching vibration) in the
3600–2800 cm21 region. Strong peaks at 1614 and 1603 cm21
are for yasCOO, medium intensity peaks at 1397 and 1382 cm21
are for ysCOO, and two strong peaks at 1539 cm21
are attributed for yas NO2. Additional peaks at 1344 and
1517 cm21 are attributed for ysNO2 and C55N, respectively.
Electrochemical Analysis
A cyclic voltammogram (CV) obtained at 0.1 V/s using
0.1 M KCl as supporting electrolyte is shown in Figure 7. The
copper complex shows one pair of well-defined and stable
redox waves in the potential range of 0.8 ꢀ 20.1 V and two
irreversible broad waves in the range of 20.2 ꢀ 20.8 V,
whereas the sharp anodic peak observed at 0.02 V is typical
FIG. 3. The crystal structural unit of complex 2.
FIG. 5. The structure of metal framework in complex 1.

STRUCTURES AND PROPERTY OF TWO NOVEL COMPLEXES
631
TABLE 4
Hydrogen bonds for complex 2 [A and deg.]
˚
D–H ꢀ ꢀ ꢀ A
D(D–H)
D(H ꢀ ꢀ ꢀ A)
D(D ꢀ ꢀ ꢀ A)
,DHA
O(8)–H(8F) ꢀ ꢀ ꢀ O(2)
O(7)–H(7E) ꢀ ꢀ ꢀ N(5)
O(7)–H(7F) ꢀ ꢀ ꢀ O(3)
O(9)–H(9F) ꢀ ꢀ ꢀ N(3)#3
O(8)–H(8E) ꢀ ꢀ ꢀ O(2)#4
O(9)–H(9E) ꢀ ꢀ ꢀ O(1)#4
0.78 (4)
0.92 (4)
0.86 (4)
0.80 (4)
0.95 (4)
0.94 (5)
1.93 (4)
1.85 (5)
1.81 (4)
2.00 (4)
1.77 (4)
1.79 (5)
2.700 (3)
2.776 (4)
2.640 (3)
2.794 (4)
2.713 (3)
2.731 (3)
168 (4)
177 (4)
162 (4)
173 (4)
171 (4)
174 (4)
Symmetry transformations used to generate equivalent atoms: #1 2x þ 2, 2y þ 1,
2z þ 1; #2 2x þ 1, 2y þ 3, 2 z þ 1; #3 2x þ 2, 2 y þ 2, 2 z þ 2; #4 2x þ 1,
2y þ 2, 2z þ 1.
for a species stripped from the electrode surface (Beatriz response can be assigned to the oxidation-reduction of copper
et al., 2001).
The effects of scan rates (y) on the peak potentials and
in the complexes (Hong and You, 2004).
Figure 6b shows the CV of Co(L) on the glassy carbon. The
the peak currents were investigated for the first redox complexes produce the irreversible cathodic wave at 20.559,
couple between 0.1 to 0.5 V/s over a reduced potential range moreover the peak currents decrease with succeeding potential
(þ0.8 to 20.1 V). The values of the formal potential E0 scans, suggesting an adsorbed species formation on the
(E0CuL ¼ 0.143 V), taken as the average of Epa and Epc, and electrode surface. However, the process at 0.505 V is also a
1
the potential separation DE ¼ Epa 2 Epc(DECuL ¼ 137 mV) successive reaction, which was confirmed by performing the
1
for the copper complex is very different due to the difference scan from 0.80 V to 0.20 V, and there is no wave, whereas
of space circumstance. The deviation from this value of DE the anodic wave is still present. The electrode reactions may
is scan-rate dependent. The variations of ipa/ipc as a function be attributed to the cobalt of the complexes (Kumita et al.,
of the scan rate were analyzed, showing the current ratio 1998; Desiraju, 1996).
change from 1.0 to 1.5 with the increase of y. The results
indicate that the species undergoes a quasi-reversible redox
process. In addition, it was found that ip is linearly proportional
to y1/2, confirming the reversible diffusion-controlled process
for the electrochemical system. From the experiment, the elec-
trode reactions are very complex, indicating that the electrode
FIG. 7. Cyclic voltammogram of complex 1, 2; (a) the cyclic voltammogram
FIG. 6. The structure of metal framework in complex 2.
of complex 1 (CuL1); and (b) the cyclic voltammogram of complex 2 (CoL2).

632
H.-B. QIAO ET AL.
EXPERIMENTAL
Road, Cambridge, CB2 1EZ, UK (fax: þ44 –1223-336033;
email: deposit@ccdc.cam.ac.uk.)
Equipment and Measurements
The chemicals for the syntheses of the compounds were all
of analytical pure grade, purchased from Zhengzhou Chemical
Reagent Company and used without further purification. IR
spectra were recorded on a Nicolt IR-470 spectrophometer as
KBr pellets in the range 4000–400 cm21. Single crystal
structure was measured on a Rigaku-Raxis-IV X-ray diffracto-
meter and thermal analyses were done with a NETZCH
DSC in air atmosphere from room temperature to 7008C.
Cyclic voltammogram was electroanalysized with CHI650
(SHANGHAI CHENHUA).
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Complex 1: 2 ml (0.5 M) aqueous solution of CuCl2 was
added to the aqueous solution containing o-phthalic anhydride
(0.07 g, 0.5 mmol), then neutralized to pH ꢁ 7 using
0.5 M KOH solution with stirring. The resulting mixture was
run into a small vial and allowed to slowly evaporate at room
temperature. A blue massive crystal suitable for single crystal
X-ray diffraction analysis was obtained in one month and
filtered, washed with anhydrous ethanol, and dried naturally.
With the same method mentioned above, purple crystals of
complex 2 is synthesized in about one month.
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X-Ray Crystallography
Intensity data of complexes 1, 2 were measured with a
Rigaku-Raxis-IV X-ray diffractometer using monochromated
˚
Mo Ka (l ¼ 0.71073 A) radiation at 291 K. Raw data were
corrected and the structure was solved using the SHELX-97
program. Non-hydrogen atoms were located by direct
phase determination and subjected to anisotropic refinement.
The full-matrix least-squares calculation on F2 were applied
on the final refinement. The refinement converged
at R1 ¼ 0.0722, wR2 ¼ 0.1925 values for reflection with
I . 2s for complex 1, and R1 ¼ 0.0447, wR2 ¼ 0.1062
values for reflection with I . 2s for complex 2. Details of
crystal structure determination are summarized in Table 1.
Full atomic data are available as a file in CIF format.
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Ruiz-Perez, C.; Sanchiz, J.; Hernandez Molina, M.; Lloret, F.;
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic Data
Centre, CCDC Nos. 237171, 249824 for compounds 1 and 2,
respectively. Copies of this information may be obtained
free of charge from The Director, CCDC, 12 Union