J Chem Crystallogr (2015) 45:476483

DOI 10.1007/s10870-015-0617-8

ORIGINAL PAPER

Crystal Structure and Behavior in Solution

of [Cu(HBPA)2]Cl24H2O [HBPA 5 (2-hydroxybenzyl-2pyridylmethyl)amine]
Nathalia F. B. Azeredo1 Erika S. Bull1 Jackson A. L. C. Resende2
Adolfo Horn Jr.1 Christiane Fernandes1

Received: 3 September 2015 / Accepted: 2 November 2015 / Published online: 16 November 2015
Springer Science+Business Media New York 2015

Abstract The crystal structure of [Cu(HBPA)2]Cl24H2O

[HBPA = (2-hydroxybenzyl-2-pyridylmethyl)amine] revealed
an octahedral geometry around Cu(II). The mononuclear
complex crystallizes in the triclinic space group P21/n with
cell lengths of a = 7.3705 (6), b = 9.7695 (6), c =
and with cell angles of a = 90, b =
20.2314 (15) A
100.264 (3) and c = 908. The coordination plane is comprised of two secondary amine and two pyridine nitrogens,
the phenol oxygen atoms are coordinated in the protonated
form and occupy the axial sites. Investigations in solution
(MeOH and DMF) by electronic spectroscopy and electrochemical studies suggest effect of the solvents on the
structure, indicating the partial coordination of the axial
ligands as phenolate, resulting in the formation of distinct
species in solution. Addition of base enables the effective
coordination of phenol group as phenolate, as observed by
the increase of the intensity of the band at 429 nm and the

Electronic supplementary material The online version of this

article (doi:10.1007/s10870-015-0617-8) contains supplementary
material, which is available to authorized users.
& Christiane Fernandes
chrisuenf@gmail.com; chrisf@uenf.br
1

Laboratorio de Ciencias Qumicas, Universidade Estadual do

Norte Fluminense, Campos dos Goytacazes, RJ 28013-602,
Brazil

Laboratorio de Difracao de Raios X, Universidade Federal

Fluminense, Niteroi, RJ 24020-150, Brazil

123

formation one only compound in DMF solution, according

to cyclic voltammetry studies.
Graphical Abstract Herein we describe the crystal
structure of [Cu(HBPA)2]Cl24H2O [HBPA = (2-hydroxybenzyl-2-pyridylmethyl)amine].The coordination plane is
comprised of two secondary amine and two pyridine
nitrogens, the phenol oxygen atoms are coordinated in the
protonated form and occupy the axial sites. Investigations
in solution by electronic spectroscopy and electrochemical
studies suggest effect of the solvent; the addition of base
enables the effective coordination of phenol group as
phenolate, resulting in one only compound in solution.

J Chem Crystallogr (2015) 45:476483

Keywords Crystal structure  Copper(II) complex  In

solution behavior  Phenol coordination  HBPA  Distorted
octahedral

Introduction
Copper is a bioessential element in all living systems
and an important co-factor for several enzymes, as the
mononuclear copper metalloenzymes amine oxidase and
galactose oxidase [1]. Copper-containing amine oxidase
(AO) act as a disulphide-linked homodimer and catalyses the oxidation of primary amines to aldehydes, with
the subsequent release of ammonia and hydrogen peroxide, which requires one copper ion per subunit and
topaquinone as cofactor [2]. Galactose oxidase (GAO) is
a fungal secretory enzyme that catalyzes the oxidation
of a range of primary alcohols to the corresponding
aldehyde, with reduction of dioxygen to hydrogen peroxide [3].
Because of its biological relevance, a large number of
copper complexes have been synthesized and screened for
anticancer activity, and some of them were found to be
active both in vitro and in vivo [4]. Furthermore, it has
been demonstrated that copper levels are elevated in the
serum of patients with prostate cancer. In this sense,
dithiocarbamate/copper complexes are effective for the
treatment of patients who are resistant to classical therapies
[5].
Due to the versatile structural features, redox behavior
and physicochemical properties, copper complexes are
being used as clinical diagnostic agents and in
chemotherapeutic applications [6, 7]. In 1994, M. Palaniandavar and co-workers reported the synthesis and
spectroscopic characterization of a copper complex with N
and O donor ligands, in order to mimic the active site of
GAO. In this study, a new mononuclear copper complex
[Cu(HBPA)Cl]H2O was obtained in the reaction between
HBPA, CuCl22H2O and NEt3, where HBPA is the ligand
(2-hydroxybenzyl-2-pyridylmethyl)amine. The proposed
square-based geometry for the copper center is supported
by EPR [8]. In this sense, Neves and co-workers reported,
in 1996, the synthesis and crystal structure of a new
mononuclear copper(II) complex: [Cu(HBPA)2](CH3
COO)23H2O [9]. In 1999, Neves and co-workers reported
the crystal structures for the ligand HBPA and for its
copper(II) complex [Cu(HBPA)2](ClO4)22H2O [10].
Herein, we report the synthesis and characterization of a
new mononuclear copper(II): [Cu(HBPA)2]Cl24H2O,
which was obtained employing [Cu(OH2)2]Cl2 instead of
[Cu(CH3COO)2]2H2O or [Cu(OH2)6](ClO4)2, as reported
previously.

477

Experimental Section
Materials and Methods
The ligand and its respective copper complex were synthesized using analytical grade reagents. In this present work,
2-(aminomethyl)pyridine, salicylaldehyde, sodium tetrafluorborate, potassium bromide (KBr), tetrabutylammonium
perchlorate (TBAClO4) were purchased from Sigma-Aldrich
and used as received. Methanol, dimethylformamide (DMF)
and isopropanol were supplied by Tedia.
Characterization and Instrumentation
Electronic spectra were recorded in MeOH and DMF on a
UVVis spectrophotometer Varian Model Cary 50 Bio,
between 200 and 1000 nm. Samples were placed in quartz
cuvettes with an optical path of 1 cm. Infrared spectra of
the synthesized compound were recorded using a Shimadzu
infrared spectrometer FT-IR 8300 in KBr pellets. The
electrical conductivity of a 1 9 10-3 M solution of the
copper complex was measured with a Biocristal conductometer in DMF and MeOH. Cyclic voltammograms (CVs)
were recorded with a PG-3901 Omnimetra potentiostat/galvanostat in DMF containing 0.1 mol dm-3
TBAClO4 as the supporting electrolyte under argon
atmosphere at room temperature. The electrochemical cell
employed was a standard three-electrode configuration: a
glassy carbon working electrode, a platinum-wire auxiliary
electrode and a platinum reference electrode. The formal
potential of the ferrocenium/ferrocene couple was 0.36 V
versus the reference electrode.
Synthesis of [Cu(HBPA)]Cl24H2O
[Cu(HBPA)2]Cl24H2O was prepared by the reaction
between the ligand (2-hydroxybenzyl-2-pyridylmethyl)
amine (HBPA) [10] (2 mmol, 428 mg) and copper(II)
chloride dihydrate (CuCl22H2O) (170 mg, 1 mmol), in
methanol. Warm salt solution was added to a hot
methanolic solution of HBPA and the reaction mixture was
stirred under reflux, for 3 h. Thereafter, the green solution
was left to stand for a few days whereupon light purplish
crystalline solid was formed. It was filtered, washed with
cold isopropanol and dried under vacuum. Yield: 0.27 g
(86 %). m.p.: 175 C. The molecular structure of this
complex is presented in Scheme 1.
X-ray Data Collection and Structure Refinement
Single crystals of copper complex suitable for X-ray
diffraction were selected and isolated from the mother

123

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J Chem Crystallogr (2015) 45:476483

Scheme 1 Synthesis of
[Cu(HBPA)2]Cl24H2O

OH
HO
NH
NH

+ CuCl2 . 2H2O

CH3OH

Cu

.2Cl.4H2O

HN
OH

Results and Discussion

Spectroscopic Studies

Fig. 1 ORTEP plot of [Cu(HBPA)2]Cl24H2O, ellipsoids at 50 % of

probability. Hydrogen atoms were omitted for clarification, except for
H-phenol, H-amine and H-water molecules

liquor. A purple block crystal with dimensions of

0.193 mm 9 0.270 mm 9 0.323 mm was mounted on a
Mitegen micromount using mineral oil. The X-ray
diffraction data was collected at 150(2) K on a Bruker D8
Venture diffractometer using MoKa radiation. Frames
were collected, indexed, processed using APEX2 [11]. The
files were scaled and corrected for absorption with
SABABS software. The crystal was kept at 150 K during
data collection. Using Olex2 [12], the structure was solved
using Direct Methods (SHELXS-13) and refined by fullmatrix methods (least-squares minimization) using
SHELXL-13 [13]. A perspective view of the cation is
displayed in Fig. 1. Detailed crystallographic information
are presented in Table 1. The bond lengths and bond angles
of this complex are listed in Table 2.

123

The IR spectrum of the complex was compared with that of

thefree ligand in the region 4000400 cm-1 [10]. The
copper complex exhibits bands at 3381 (m NH aminic),
1612 and 1566 (m C = N py) and 1365 cm-1 (d OH phenol) (Fig. 2). For the ligand, these bands are observed at
3263, 1593, 1566 and 1352 cm-1. The presence of the d
OH in the spectrum of the complex suggests that the phenol
group remains protonated after the coordination with the
copper center.
The UVVis spectrum of the complex was measured
DMF and MeOH. As previously described by Neves and
co-workers, we also detected a color change in the solution,
from purple to green in the presence of DMF, thus indicating the coordination of the solvent molecule to the
copper center. This could be due to weak interactions
between the phenol groups and the metal center, since the
coordinated phenol groups are in the protonated form [10].
The complex exhibits two bands in DMF, at 429
(e = 341 dm3 mol-1 cm-1) and at 661 nm (e = 163 dm3
mol-1 cm-1). Similarly, in MeOH, these transitions were
observed at 422 (e = 246 dm3 mol-1 cm-1) and 644
(e = 105 dm3 mol-1 cm-1), indicating the effect of solvent. The ligand HBPA showed bands at 269
(e = 4.4 9 103 dm3 mol-1 cm-1) and at 283 nm
(e = 2.84 9 103 dm3 mol-1 cm-1), which could be
attributed to the p ? p* transition.
The electronic transitions observed in the visible range
in other similar copper complexes, e.g. [Cu(HBPA)2X2]
(X = ClO4-, OAc-, NO3-, SO42-) had been attributed to
the dd transitions [10]. For these previously reported
complexes, the transition at lower energy was insensitive to
the counter ions, showing absorption around 640 nm.
However, the band at higher energy underwent a blue shift
in the presence of the counter ion OAc- (405 nm) when
compared with ClO4-, NO3-, SO42- (*428 nm), For our
compound, the presence of the counterion chloride did not

J Chem Crystallogr (2015) 45:476483

479

Table 1 Crystal data and structure refinement for the copper

complex

Table 2 Selected geometrical parameters (bond lengths and angles)

of copper complex

Molecular formula

[Cu(C26H32N4O4)] Cl24H2O

Length

Formula weight

635.03

Atom

Atom

)
Length (A

Crystal system

Monoclinic

Cu1

N2

2.026 (3)

Space group
)
a (A

P21/n

Cu1

N2(i)

2.026 (3)

7.3705 (6)

)
b (A
)
c (A

Cu1

N1

2.013 (3)

9.7695 (6)

Cu1

N1(i)

2.012 (3)

20.2314 (15)

Cu1

O1

2.547 (2)

b ()
3)
Volume (A

100.264 (3)
1433.47 (18)

Cu1

O1(i)

2.547 (2)

qcalcg (cm3)

O1
N2

C13
C7

1.376 (4)
1.495 (4)

1.471

l (mm-1)

N2

C6

1.481 (4)

0.995

N1

C5

1.351 (4)

Tmin, Tmax

0.606, 0.745

N1

C1

1.348 (4)

F(000)

662.0

2H range for data collection ()

5.6250.7

Index ranges

-8 B h B 8, -11 B k B 11,
-19 B l B 24

Reflections collected

8225

Independent reflections

2602 [Rint = 0.0372,

Rsigma = 0.0369]

Angle
Atom
N2

(i)

Atom

Atom

Angle (deg)

Cu1

N2

180
(i)

98.25 (11)

N1

Cu1

N2

N1(i)

Cu1

N2

98.26 (11)

Cu1

N2(i)

81.75 (11)

Observed reflections (I [ 2r(I)]

2226

N1(i)

Number of parameters

179

N1

Cu1

N2

81.75 (11)

Cu1

N1

180

1.151

N1(i)

Final R indexes [I C 2r (I)]

R1 = 0.0455, wR2 = 0.0986

O1(i)

Cu1

O1

180

Final R indexes [all data]

R1 = 0.0567, wR2 = 0.1025

O1

Cu1

N1

91.17 (10)

0.89/-0.41

O1

Cu1

N2

86.23 (9)

O1

Cu1

N1(i)

88.84 (10)

Cu1

N2(i)

93.77 (9)

Cu1

N1(i)

91.16 (10)

(i)

Goodness-of-fit on F

-3)
Largest diff. peak/hole (e A

O1

show any effect on the energy of both the transitions when

compared with the compounds containing ClO4-, NO3-,
SO42-.
The transition observed at 429 nm shows an e value
(341 dm3 mol-1 cm-1) a little bit high for a typical dd
transition. In order to evaluate if it is really a dd transition,
Et3N, a base, was added to the respective solution, and
Fig. 3 ilustrates the spectra before and after the addition of
the base. The addition of a few drops of Et3N to a solution
of the copper complex, in DMF, has resulted in an increase
of the intensity of the band at 429 nm, thus suggesting that
it is a phenolate pp ? Cu2? dr* charge transfer, as a result
of the deprotation of the phenol group. The band at 661 nm
did not show any increase in the intensity, which support
that it is a dd transition. In the absence of base but in the
presence of solvents like DMF or MeOH the LMCT is
present, thus indicating the partial deprotonation of the
phenol groups and its coordination to the copper center in
the form of a phenolate. This result indicates the presence
of distinct compounds in solution, suggesting that the solid
state structure is not preserved in solution and it is solvent
dependent. It is also in good agreement with the

O1

(i)

O1

(i)

Cu1

N2

O1(i)
O1(i)

Cu1
Cu1

N1
N2

86.23 (9)
88.83 (10)
93.77 (9)

Symmetry codes (i) 2-x,1-y,1-z

conductimetry measurements which suggest that the solid

state structure is not preserved in solution (see below). On
the other hand, it differs from the interpretation described
previously [10], which classify this band as a dd
transition.
Crystal Structure Determination of copper complex
The [Cu(HBPA)2]Cl24H2O complex consists of a distorted
octahedral ion, with the two tridentate donor ligand binding
to the copper(II) center with a N4O2 donor environment in
a facial coordination arrangement. The copper(II) is located about the center of symmetry, so the asymmetric unit
consists of half of the complex, a chloride ion and two
water molecules of crystallization. The nitrogen atoms are

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J Chem Crystallogr (2015) 45:476483

Transmittance (%)

480

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )
Fig. 2 IR spectra: HBPA (top) and copper complex (bottom)

-1

Absorbance

6x10

in the equatorial plane while axial positions are occupied

by the oxygen atoms. The average copper-nitrogen distance
and the distance between copper-oxygen is
is 2.019 (7)A
. Thus, the JahnTeller Theorem can be used to
2.547 (2)A
explain the distortion in the system. Possibly this effect is
intensified by the fact that the phenolic group remains
protonated after the coordination to the copper center, like
described by Rey and co-workers [14]. pp stacking
between the pyridine and phenolic ring of two complementary ligands in the complex was also observed, with a
(Fig. 4).
distance between centroids of 3.655 A
The crystal packing is stabilized by a supramolecular
system formed by moderate hydrogen bonds and p-p
stacking along the (001) plane. The H-bond system forms
chain and rings with graph-set notation C 8C6
h
i
R1666 R1266 R1044 R844 (Figs. 5 and 6). The interaction system composed of O1O1wO2w(x, 1-y, z)
N2(x, 1-y, z) results in C(8) chain along [010] while the
interactions ClO2w(2-x,-y,1-z) O1w(2-x,-y,1-z) 
Cl(1?x, y, z) forms the C(6) chain in [100] direction. Table 3
presents the hydrogen bonding geometry for this complex.

Electrochemical Studies
-1

4x10

B
-1

2x10

400

500

600

700

800

900

Wavelenght (nm)
Fig. 3 Electronic spectra of the copper complex. a After addition of
ET3N to the copper complex in DMF; b Before addition of Et3N to
the copper solution

Fig. 4 Intramolecular pp

stacking interaction

123

The electrochemical characterization of the compound

was performed employing conductivimetry and cyclic
voltammetry analyses. The conductivity measurements
in MeOH (130 lS cm-1) suggest that the complex is
cationic in solution (2:1 electrolyte type). However, in
DMF (51 lS cm-1) the value is lower than that expected
[15] and they are not in agreement with the crystallography data, which show that this compound has two
chloride counterions. These results indicate the partial
coordination of phenol groups in solution, thus reducing
conductivity.

J Chem Crystallogr (2015) 45:476483

Fig. 5 Ring representation of the H-bonds present in this structure

Based on the conductivimetry measurements, it is proposed that the coordination sphere for the copper center is
not preserved in MeOH and DMF solution, which further
substantiated the coordination of phenolate groups with
copper. In this sense, cyclic voltammetry was employed in
order to get some insights about the behavior of this
complex in solution. The cyclic voltammogram of the
copper complex in DMF is presented in Fig. 7, which
indicates the presence of one cathodic process at -0.840 V

481

versus Fc/Fc?, that can be attributed to the Cu(II)/

Cu(I) redox couple. This potential is about 0.1 and 0.260 V
more positive than those reported by the same compound
containing other counterions (ClO4- and OAc- respectively) [10]. This means that the counterion can interact
with the metal center in solution, mainly in the case of the
acetate, probably by displacing the phenol groups. Two
anodic processes are observed at -0.110 and at 0.260 V
versus Fc/Fc?, which could be attributed to the oxidation
of the Cu(I) complex. The presence of two anodic waves
indicates the presence of two Cu(I) complexes in solution
due to the release of phenol group from the coordination
sphere, after the reduction to Cu(I). Tetrabutyl chloride was
added to the solution to evaluate if one of these processes
could be related to the presence of the counterion chloride.
However, as seen in Fig. 7b, no change in the intensities of
the signal was observed, which indicates that these two
oxidative waves are related to the presence of two copper
complexes in solution, as previously indicated the UVVis
and conductivimetric studies. It is importante to highlight
that the cyclic voltammetry carried out with the compounds
containing perchlorate and acetate showed just one process.
To have more insights about the oxidative processes
observed for our copper complex, we carried out the
electrochemical study in the presence of Et3N. It resulted in
a cathodic shift of the reduction process, which is observed
at -1.04 V versus Fc/Fc?. This observation indicates a

Fig. 6 Supramolecular system

(001) plane

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J Chem Crystallogr (2015) 45:476483

Table 3 Hydrogen bonding

geometry of the copper complex

DHA

)
DH (A

)
HA (A

)
DA (A

DHA ()

O1H1O1W

0.84

1.83

2.662 (3)

168.2

N2H2O2W

0.93

1.99

2.856 (3)

153.2

O1WH1WACl1

0.87

2.29

3.145 (3)

168.2

O1WH1WBCl1(i)

0.87

2.23

3.076 (3)

165.0

0.87

2.27

3.130 (3)

170.0

0.87

2.01

2.860 (3)

164.6

O2WH2WACl1(ii)
O2WH2WBO1 W

(iii)

Symmetry codes (i) x ? 1, -y, -z ? 1; (ii) x ? 2, -y ? 1, -z ? 1; (iii) x, y ? 1, z

chloride as counterion. Investigations of the behavior of

this complex in solution by electrochemical studies (conductimetry and cyclic voltammetry) and electronic spectroscopy indicated that this structure is not preserved, due
to partial coordination of the phenol groups as phenolates,
thus resulting in the formation of at least two distinct
species in solution. However after the addition of Et3N,
only the phenolate copper complex was observed. This
paper represents the need of careful investigation in solution for complexes containing protonated phenol groups.

C
B

Supplementary Materials

A
-2x10

-1x10

-5x10

-1

5x10

-1

1x10

E (V)
Fig. 7 Cyclic voltammograms of the copper complex. a in DMF; b in
DMF with addition of ammonium tetrachloride; c in DMF with
addition of Et3N

decrease in the Lewis acidity of the copper center which is

a result of deprotonation of the phenol groups and their
coordination as phenolate (a better Lewis donor). This
cathodic process can be attributed to the Cu(II)/Cu(I) redox
couple. Furthermore, after the addition of the base Et3N,
just one anodic process is observed at 0.100 V versus Fc/
Fc?, that is attributed to the process Cu(I) ? Cu(II). The
cathodic and anodic processes are far apart, indicating an
irreversible electrochemical behavior. The difference in the
redox potential for the cathodic process after the addition
of Et3N is almost 200 mV more negative. Thus, it is easier
to reduce the copper complex before the addition of Et3N,
which in turn explained the effective coordination of the
phenolate groups after the addition of ET3N.

This data CCDC: 1421894 can be obtained free of charge

at www.ccdc.cam.ac.uk.conts/retrieving.html/ or from the
Cambridge Crystallographic Data Centre (CCDC), 12
Union Road, Cambridge CB2 IEZ, UK; fax: ? 44(0)
1223-336033; e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgments The authors are grateful to financial support
received from FAPERJ (Fundacao de Amparo a` Pesquisa do Estado
do Rio de Janeiro) and CNPq (Conselho Nacional de Desenvolvimento Cientfio e Tecnologico).

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