Syntheses, crystal structures, and properties of Cu(II) and Zn(II) complexes with an asymmetric tripodal ligand

Article abstract of DOI:10.1080/00958972.2012.746459

[Cu₂L₂](ClO₄)₂ (1) and [Zn ₂L₂](ClO₄)₂ (2) (HL = 2-[bis(3-aminopropyl)amino]propanol) have been synthesized and characterized. X-ray crystallography analyses show that

Full text of DOI:10.1080/00958972.2012.746459

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Syntheses, crystal structures,
and properties of Cu(II) and Zn(II)
complexes with an asymmetric tripodal
ligand
a b
a
a
WENWU SUN
, QINGRONG CHENG , HONG ZHOU & ZHIQUAN
a
PAN
a
National Engineering Research Center of Phosphate Resources
Development and Utilization Wuhan Institute of Technology,
Wuhan, P.R. China
b
State Key Laboratory of Phytochemistry and Plant Resources
in West China, Kunming Institute of Botany, Chinese Academy of
Sciences, Kunming, P.R. China
Accepted author version posted online: 06 Nov 2012.Version of
record first published: 12 Dec 2012.
To cite this article: WENWU SUN , QINGRONG CHENG , HONG ZHOU & ZHIQUAN PAN (2013):
Syntheses, crystal structures, and properties of Cu(II) and Zn(II) complexes with an asymmetric
tripodal ligand, Journal of Coordination Chemistry, 66:1, 56-65
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Journal of Coordination Chemistry
Vol. 66, No. 1, 10 January 2013, 56–65
Syntheses, crystal structures, and properties of Cu(II) and
Zn(II) complexes with an asymmetric tripodal ligand
A,B
A
A
A
WENWU SUN , QINGRONG CHENG , HONG ZHOU * and ZHIQUAN PAN *
a
National Engineering Research Center of Phosphate Resources Development and
b
Utilization, Wuhan Institute of Technology, Wuhan, P.R. China; State Key Laboratory of
Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese
Academy of Sciences, Kunming, P.R. China
(Received 29 May 2012; final version received 3 October 2012)
[
2 2 4 2 2 2 4 2
Cu L ](ClO ) (1) and [Zn L ](ClO ) (2) (HL= 2-[bis(3-aminopropyl)amino]propanol) have been
synthesized and characterized. X-ray crystallography analyses show that both are dinuclear with
bis-μ-alkoxy-bridged structures. Their molecular structures are centro-symmetric. Each metal adopts
a trigonal bipyramidal coordination. Cyclic voltammetry indicates that 1 undergoes two irreversible
redox processes with big potential differences (EpaꢀEpc) and ratio of ipa/ipc, while only one reduc-
tion peak is observed in 2. Magnetic susceptibility shows that there is a strong antiferromagnetic
ꢀ1
interaction (J = ꢀ69.4(4) cm ) between the two copper(II) centers in 1. Hydrolysis activities
toward 4-nitrophenyl acetate of the two complexes have been investigated and second-order rate
ꢀ2
ꢀ2
ꢀ1 ꢀ1
M s in 10% (v/v) CH
constants of 1 and 2 are (4.3 ± 0.3) ꢁ 10 and (3.1 ± 0.2) ꢁ 10
3
CN
aqueous solution at 25 °C.
Keywords: Dinuclear Cu(II) and Zn(II) complexes; Crystal structure; Electrochemistry; Magnetic
property; Hydrolysis activity
1. Introduction
Modeling studies on metalloenzymes have been explored for application in medicine and
industry and to understand the mechanism of metalloenzymes in biological systems [1].
Research on hydrolytic mechanisms of the natural hydrolysis enzymes shows that attack of
nucleophiles to electrophilic substrates is the key process [2]. Kinetics of ZnL-promoted
4-nitrophenyl acetate (NA) hydrolysis shows that Zn(II)-bound alkoxide can generate a
strong nucleophilic attack toward carboxy ester, which is responsible for higher hydrolysis
activity of complexes [3]. Alkoxy-bridged complexes with N O coordination have higher
3
2
hydrolysis activities, which vary with the structural difference [4]. Some tripodal ligands hav-
ing N O coordination with N(R–NH ) (R–OH) (where R=CH CH or CH CH CH ) have
3
2 2
2
2
2
2
2
been synthesized and characterized [5]; however, few studies of hydrolysis activity mimics or
physical chemistry properties of this kind of complexes were reported [4a, 5]. There is still a
challenge to synthesize small molecules having high activity of metalloenzymes and to reveal
the effect of structure on the hydrolysis activities of model compounds [6].
*
Corresponding authors. Email addresses: hzhouh@126.com (H. Zhou); zhiqpan@163.com (Z.Pan)
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online Ó 2012 Taylor & Francis
http://dx.doi.org/10.1080/00958972.2012.746459

Cu(II) and Zn(II) Complexes of Tripodal Ligands
57
To explore the effect of tripodal ligands and metal ions on the structures and properties
of such complexes, we prepared two new dinuclear Cu(II) and Zn(II) complexes using
2-[bis(3-aminopropyl)amino]propanol) as tripodal ligands, Scheme 1. Herein, the
syntheses, crystal structures, electrochemical properties, magnetic properties and hydrolysis
activities toward NA of 1 and 2 are reported.
2
. Experimental
2
.1. Materials and measurements
All solvents and chemicals were of analytical grade and used as received, except methanol
that was purified to anhydrous by general method. Elemental analyses were obtained on a
Perkin-Elmer 240 analyzer. Cyclic voltammograms were recorded on a CHI 750B electro-
chemical analyzer, and the measurements were taken in H O solutions
2
ꢀ
4
ꢀ3
ꢀ3
(
5 ꢁ 10 mol dm ) of the complex containing 0.1 mol dm tetraethylammonium perchlo-
rate as the supporting electrolyte. A three-electrode cell equipped with a glass carbon
working electrode, a platinum wire as the auxiliary electrode and a saturated calomel elec-
ꢀ1
trode as the reference were used. Scanning rates were 100 mVs . The solution was deaer-
ated for 15 min before measuring. Magnetic susceptibility of a crystalline-powdered
sample was measured on a Quantum Design MPMS-XL SQUID magnetometer from 2.0
to 300 K and the diamagnetic corrections were made according to Pascal’s constants.
Scheme 1. Preparation of the tripodal ligand.
Scheme 2. Proposed catalytic mechanism.

5
8
W.W. Sun et al.
2
.2. Synthesis of [Cu L ]2ClO (1)
2 2 4
2
7
2
-[Bis(3-aminopropyl)amino]propanol was prepared by our previous method [7]. Yield,
1
2%. H NMR (D O, TMS as reference): d0.941 (d, 3H, CH C), 1.380 (m, 4H, CH ),
2
3
2
.315 (m, 10H, CH ), 3.742 (m, 1H, CH), 4.664 (d, 1H, OH). Anal. Calc. for C H N O :
2
9 27 3 3
C, 48.0; H, 12.1; N, 18.6. Found: C, 48.4; H, 12.5; N, 18.3.
Anhydrous methanol (15 mL) solution of 2-[bis(3-aminopropyl)amino]propanol (0.094 g,
.5 mmol) was added dropwise to anhydrous methanol solution (10 mL) of Cu(ClO ) ·6H O
0
4
2
2
(0.186 g, 0.5 mmol). The mixture was stirred for 24 h at room temperature and filtered with
blue-green block crystals of [Cu L ]·2ClO suitable for X-ray diffraction obtained by slow
2
2
4
evaporation of the resulting filtrate for several days at ambient temperature. Yield, 61%.
Anal. Calc. for C H N Cl Cu O : C, 30.8; H, 6.3; N, 12.0. Found: C, 31.2; H, 6.2; N,
1
8
44
6
2
2 10
–
1
ꢀ
4
1
1.9. IR (KBr, cm ): 3284, 3321 (N–H), 3456 (O–H), 1096 (ClO ).'
2
.3. Synthesis of [Zn L ]2ClO (2)
2 2 4
This compound was prepared by a similar procedure as described above, except that
Zn(ClO )·6H O was used instead of Cu(ClO ) ·6H O. The obtained crystals suitable for
4
2
4 2
2
X-ray diffraction are colorless prisms. Yield, 53%. Anal. Calc. for C H N Cl Zn O : C,
1
8
44
6
2
2 10
–
1
3
(
0.6; H, 6.3; N, 11.9. Found: C, 30.9; H, 6.2; N, 12.1. IR (KBr, cm ): 3289, 3329
N–H), 3449 (O–H), 1095 (ClO4 ). Caution: Although no problem was encountered in
ꢀ
this work, transition metal perchlorates are potentially explosive and should be handled in
small quantities.
2
.4. X-ray crystallography
Diffraction intensity data were collected on a SMART-CCD area-detector diffractometer at
93 K using graphite monochromated Mo K radiation (λ = 0.71073 Å). Data reduction and
2
α
cell refinement were performed by SMART and SAINT [8]. The structures were solved by
2
direct methods (Bruker SHELXTL) and refined on F by full-matrix least squares (Bruker
SHELXTL) using all unique data [9]. The non-H atoms in the structure were treated as
anisotropic. Hydrogens were located geometrically and refined in riding mode.
2
.5. Kinetic studies
Catalytic hydrolysis rates of NA by the complexes were measured by a similar method
described in the literature [5]. Buffer solution containing 20 mM Tris–HCl (pH 6.8–8.8)
ꢀ
1
was used and the ionic strength was adjusted to 0.1 mol L with NaNO solution. NA
3
and the complexes were mixed in the buffer solution and release of 4-nitrophenolate in
1
0% CH CN (v/v) aqueous solution at 25 °C was recorded by UV-2450 spectrophotometer.
3
ꢀ
1
[
NA] was set to be constant, and the observed first-order rate constant k
(s ) was
obsd
2
+
measured in the presence of various concentrations of [M L ] (1–3 mM). The kobsd was
2
2
calculated from the decay slope (4-nitrophenolate release rate/[NP]). The second-order rate
constant for NA hydrolysis was calculated from kobsd/[complex]total [4a].

Cu(II) and Zn(II) Complexes of Tripodal Ligands
. Results and discussion
.1. Synthesis and spectral properties
59
3
3
A blue-green dinuclear copper(II) complex and a colorless dinuclear zinc(II) complex were
obtained by reaction of 2-[bis(3-aminopropyl)amino]propanol and M(ClO ) ·6H O (M=Cu
4
2
2
–
1
or Zn) in methanol solution. In the IR spectrum of 1, signals at 3284 and 3321 cm are
–
1
assigned to the N–H stretch. The presence of a broad band at 3456 cm is characteristic
–
1
of OH groups [5a]. A symmetrical band at 1096 cm indicates the presence of uncoordi-
nated perchlorate [10]. The IR spectrum of 2 is similar to that of 1, and assignments for
the characteristic vibrations of 2 are the same as for 1.
3
.2. Description of the crystal structure
Perspective views of the molecular structures for 1 and 2 are shown in figure 1 with atom
numbering scheme. Crystallographic data and details about the data collection are
presented in table 1. Selected bond distances and angles relative to copper(II) and zinc(II)
coordination spheres are listed in table 2.
2
+
3
.2.1. Crystal structure of l. The crystal structure of 1 consists of [Cu L] and two
2
non-coordinated perchlorates. The molecular structure is centrosymmetric in which the
center is located at the middle of two Cu(II) ions. The Cu(II) ions are connected by two
μ2-hydroxypropane-bridged groups with Cu-Cu distance of 2.969(1) Å and Cu(1)-O(1)-Cu
Figure 1. Structural depiction of 1(a) and 2(b).

6
0
W.W. Sun et al.
Table 1. Crystal data and structure refinement for 1.
Empirical formula
Formula weight
Crystal system
Space group
a, b, c (Å)
C
18
H
44Cl
2
Cu
2
N
6
O
10
C
18
H
44Cl
2 6
N O10Zn
702.57
Orthorhombic
Pnn2
11.859(3), 13.311(3), 9.273(2)
90.00, 90.00, 90.00
1463.8(6)
706.23
Monoclinic
P2(1)/n
7.9671(6), 15.2489(12), 2.1407(10)
90.00, 98.15, 90.00
1460.2(2)
a; b; c(°)
3
Volume (Å )
3
Z , Dcalc (g/cm )
2, 1.594
2, 1.606
μ (Mo-Ka) (mm), F(0 0 0)
Crystal size (mm)
Temperature (K)
Mo Ka radiation (Å)
h Range (°)
1.693, 732
20 9. 21 0 ꢁ 0.22 ꢁ 0.26
0.71073
2.3–26.0
1.884, 736
20 9. 21 0 ꢁ 0.22 ꢁ 0.26
0.71073
2.2–26.0
ꢀ9 ꢂ h ꢂ 6; ꢀ18 ꢂ k ꢂ 18;
ꢀ14 ꢂ l ꢂ 14
8268, 2852, 0.040
2369
Data set
ꢀ14 ꢂ h ꢂ 14; ꢀ12 ꢂ k ꢂ 16;
ꢀ
11 ꢂ l ꢂ 10
Total, uniq. data R(int)
Observed data [I > 2.0 sigma(I)]
Nref, Npar
8058, 2716, 0.055
2130
2716, 173
2852, 173
R, wR2, S
Max. and av. shift/error
0.0558, 0.1203, 1.01
0.00, 0.00
0.0474, 0.1091, 1.03
0.00, 0.00
Min. and max. resd. dens.
ꢀ0.60, 0.38
ꢀ0.66, 0.30
3
(
e/Å )
Table 2. Selected structural data for 1 and 2.
1
2
Bond
Length (Å)
Bond
Length (Å)
i
i
Cu1–O1
Cu1–O1
Cu1–N1
Cu1–N2
Cu1–N3
1.914(4)
1.975(4)
2.048(5)
2.105(7)
2.122(7)
Zn1–O1
Zn1–O1
Zn1–N1
Zn1–N2
Zn1–N3
2.089(3)
1.958(3)
2.232(3)
2.042(3)
2.054(3)
Bond angles
O1–Cu1–O1
O1–Cu1–N1
O1–Cu1–N2
N1–Cu1–N2
O1–Cu1–N3
Values (°)
76.71(18)
87.92(18)
137.0(3)
96.4(3)
Bond angles
O1–Zn1–N1
O1–Zn1–N2
N1–Zn1–N2
O1–Zn1–N3
N1–Zn1–N3
Values (°)
82.91(12)
122.32(13)
96.53(13)
119.43(15)
94.3(3)
i
126.9(2)
(
1) angle of 99.52(1)°, comparable to those of similar binuclear Cu(II) complexes of this
type [5b]. Each Cu(II) is trigonal bipyramidal with the basal plane composed of two pri-
mary amine nitrogens N2 and N3 and a bridging hydroxypropane oxygen O1; the apical
positions are occupied by a tertiary nitrogen N1 and the other bridging hydroxypropane
oxygen O1. The angle of N1–Cu1–O1 is 97.92(1)°. The average distances are Cu–O
1
.945 Å and Cu–N 2.099 Å, which are very close to similar ones in a hydroxylethyl-
bridged dinuclear copper(II) complex [5b]. The mean plane deviation of the plane consist-
ing of two copper(II) and two bridged hydroxypropane oxygens is 0.174(3) Å, indicating
that the four atoms are located in a distorted plane.
Perchlorates in the lattice join adjacent dinuclear units by hydrogen bonds to form a sad-
dle configuration, where each perchlorate is a hydrogen bond acceptor to three dinuclear
units through C–H–O and N–H–O (figure 2). The relative parameters are listed in table 3.

Cu(II) and Zn(II) Complexes of Tripodal Ligands
61
2+
2
Figure 2. View of the hydrogen bonded interactions between one perchlorate with three [Cu L] groups in 1.
3.2.2. Crystal structure of 2. Except for different metal ions, Cu for 1, and Zn for 2, 1
and 2 have the same composition and similar coordination, figure 1(b). In 2, Zn–Zn sepa-
ration is 3.106(9) Å, and Zn(1)–O(1)–Zn(1) angle is 100.16(11)°, slightly larger than in 1.
The coordination number, polyhedron and composition related to the coordination environ-
ment of the metal ions are the same. The Zn–N and Zn–O distances are in the range of
similar complexes [11]. The stacking pattern of 2 (figure 3) shows that oxygens of each
perchlorate anion have hydrogen bonding interactions with three adjacent cations, similar
to that of 1. The hydrogen bonds involve C–H–O and N–H–O, and relative parameters are
listed in table 3.
3
.3. Electrochemical studies
Electrochemical properties of 1 and 2 have been studied by cyclic voltammetry in distilled
water containing 0.1 M KCl. Typical cyclic voltammograms of 1 and 2 are given in
Supplementary material. For 1, when scanning from 0.5 to ꢀ1.2 V at a scan rate of
ꢀ1
0
.1 Vs , there are two anodic peaks (E = 0.053 V and E = 0.262 V) and cathodic
pa1 pa2
peaks (Epc1 = ꢀ0.658 V and Epc2 = ꢀ0.260 V). The separations of the anodic and cathodic
Table 3. Hydrogen bonds parameters for 1 and 2.
D–H…A
d(H–A)
D(D–A)
\DHA
1
2
N3–H3C…O5
C3–H3A…O3
C4–H4A…O2
C8–H8A…O2
N2–H2C…O3
N2–H2D…O2
N3–H3C…O5
C4–H4A…O4
C9–H9C…O2
2.4700
2.5900
2.4600
2.4900
2.2300
2.2400
2.3200
2.5000
2.5800
3.226(9)
3.052(10)
3.417(10)
3.331(9)
3.100(4)
3.124(4)
3.184(4)
3.435(5)
3.443(6)
142.00
110.00
168.00
144.00
163.00
166.00
162.00
162.00
150.00

6
2
W.W. Sun et al.
2+
2
Figure 3. View of the hydrogen bond interactions between [Zn L] and a perchlorate in 2.
peak potential of 711 and 522 mV, respectively, and the ratio of anodic to cathodic peak
currents, i /i = 2.5, indicate that redox processes are irreversible [10a]. The irreversibility
pa pc
of the redox process can be contributed to instability of Cu(I) within the strong ligand field
generated by the alkoxide and amine [11].
The cyclic voltammogram of 2 was obtained by the same experimental conditions. The
electrochemical behavior of 2 (Supplementary Material) is quite different from that of 1.
Considering that the complexes have same ligands with same coordination composition,
the difference of electrochemical properties can be assigned to the different metal ions in
ꢀ
1
the complexes. When scanning from 1.0 to ꢀ1.2 V at a scan rate of 100 mV s , only one
reduction process was observed at E = ꢀ0.668 V; no oxidant wave was found when
pc
rescanned, indicating an irreversible electrode process, in agreement with the results of
similar dinuclear Zn(II) complexes [5a].
3
.4. Magnetochemistry
The temperature dependence of the magnetic susceptibility of 1 from 2.0 to 300 K is
shown in figure 4 in the form of v T vs. T. The v T value gradually decreases with
m
m
decline of temperature, indicating the presence of antiferromagnetic interaction between
copper(II) ions in the complex. The magnetic susceptibility is fit by an expression given in
equation (1), which is based on the general isotropic exchange (Ĥ = ꢀ2 JŜ ·Ŝ ), with
1
2
S = S = 1/2 [12].
1
2
2
Ng2b2
1
vm ¼
ꢁ
ð1Þ
3 þ eꢀ
2J=kT
kT
χm is the paramagnetic susceptibility, g is the average gyromagnetic ratio; the other
symbols have their usual meanings. The best set of parameters obtained for 1 by using the
ꢀ1
above model is as follows: J = ꢀ69.4 (4) cm , g = 2.00 (0) with a coefficient of determina-
tion of R = 4 ꢁ 10ꢀ . The J value is very close to those of other dinuclear cooper(ІІ)
5

Cu(II) and Zn(II) Complexes of Tripodal Ligands
63
m
Figure 4. Experimental and calculated plots of χ T vs. T. The solid line shows the best fit with equation (1).
complexes, suggesting a strong antiferromagnetic interaction between the two copper(II)
centers [13]. However, the magnetic interactions in 1 are much smaller than those of our
previous reported macrocyclic dinuclear copper(II) complexes [12, 14]. Considering that
the Cu–Cu distance in 1 is very close to those of the macrocyclic complexes, the magnetic
difference can be mainly assigned to the magnetic pathway. For the macrocyclic
complexes, copper and two bridged phenoxides are almost in one plane, leading to effec-
tive overlap for the magnetic interactions, while in 1, the bridged oxygens and two copper
(II) ions are in a distorted plane, decreasing the magnetic interactions due to less overlap
of the magnetic pathway.
3
.5. NA hydrolysis promoted by [Cu L ](ClO ) and [Zn L ](ClO )
2 2 4 2 2 2 4 2
Reactivity of the two complexes toward hydrolysis of phosphomonoesters or carboxy ester
has also been investigated. Since no obvious hydrolysis activity of the phosphomonoesters
promoted by the two complexes was observed, the hydrolytic cleavage of NA by the
complexes is reported herein. The activity has been investigated by monitoring the hydro-
lysis of NA promoted by [Cu L ](ClO ) and [Zn L ](ClO ) at different concentrations
2
2
4 2
2
2
4 2
(1.0–3.0 mM) in the pH range 6.7–8.8. The dependence of observed pseudo-first-order rate
constants (kobs) for hydrolysis of NA on pH and on total concentration of the complexes
are shown in Supplementary Material and figure 5. The results show that kobs increases
with pH, and kobs is almost unchanged when pH is larger than 8.5 with maximum kobs at
pH = 8.8. So, pH of 8.8 was chosen to conduct hydrolysis measurements. The second-order
ꢀ
2
ꢀ2
ꢀ1 ꢀ1
rate constant KNA for 1 and 2 is (4.3 ± 0.3) ꢁ 10 and (3.1 ± 0.2) ꢁ 10
M s , calcu-
lated from the slope of the straight line k vs. [complex]. The constants of 1 and 2 are
obs
2
.1 and 1.47 times greater than that of a double hydroxyethyl-bridged dizinc complex
[4b], but lower than those of the corresponding Zn(II)-bound alkoxide complexes [3b, 4a,
1
5]. According to the literature [4a], hydrolysis activity of the double alkoxide-bridged
ꢀ
complexes is from cleavage of the bridged-alkoxide followed by binding of OH to form
the active species, which is affected by the stability of the double alkoxide-bridged struc-
tures in the complexes. 1 and 2 contain two 3-aminopropyl moieties in their structure,
which is more flexible than two 2-aminoethyl moieties in zinc(II) 2-[bis(2-aminoethyl)
amino]ethanol complex (3). The more flexible structures of 1 and 2 make them more

6
4
W.W. Sun et al.
Figure 5. Dependence of kobs on total concentration of the complexes at pH 8.8 with ionic strength 0.1 M
NaNO ) in the presence of 10% (v/v) CH CN, correlation coefficient > 0.99. The effect of the spontaneous
(
3
3
hydrolysis for buffer solution has been eliminated. (a) for 1 and (b) for 2.
stable than 3, and the steric hindrance caused by CH in 1 and 2 also hinders the binding
3
ꢀ
of OH , therefore, the hydrolysis activities of 1 and 2 are smaller than that of 3 having
similar structure with 1 and 2. The suggested catalytic mechanism of the complexes is
shown in Scheme 2. The deprotonated hydroxypropyl pendants can nucleophilically attack
acyl carbon of NA, while a hydrogen of water bound to the metal ion acts as a receptor
for the leaving group, 4-nitrophenol anion. Then the metal-bound hydroxide is a nucleo-
phile to attack the “acyl” to recycle the hydrolysis [3a].
4
. Conclusion
The reaction of 2-[bis(3-aminopropyl)amino]propanol and M(ClO ) ·6H O (M=Cu or Zn)
4
2
2
in methanol gives two hydroxypropane-bridged dinuclear complexes. Except for the differ-
ence of metal ions, the two complexes have same coordination number, polyhedron and

Cu(II) and Zn(II) Complexes of Tripodal Ligands
65
composition as well as similar hydrogen-bonding interactions between the cations of the
complexes and perchlorate anions. Due to the difference of metal ions in the complexes,
they have different electrochemical behavior. The magnetic interaction in 1 shows that
hydroxypropane-bridged dicopper(II) complex has strong antiferromagnetic interactions,
but the magnitude is smaller than those of phenoxide-bridged dicopper complexes. The
two complexes have hydrolysis activities toward NA.
Supplementary data
Full lists of crystallographic data have been deposited with the CCDC as file numbers
CCDC 880852 for 1 and 880853 for 2.
Acknowledgements
We are thankful for the financial support from the National Nature Science Foundation of
China (21171135, 20971102 and 20871097).
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