Synthesis and crystal structure of a 3D supramolecular copper(II) complex with 1-(3-{[(E)-3-bromo-5-chloro-2-hydroxybenzylidene]amino}phenyl) ethanone oxime

Article abstract of DOI:10.1080/15533174.2012.740756

A new Cu(II) complex, [Cu(L)₂], has been synthesized via the complexation of copper(II) acetate monohydrate with a new oxime-type ligand (HL = 1-(3-{[(E)-3-bromo-5-chloro-2-hydroxybenzylidene]amino}phenyl)ethanone oxime). X-ray crystallographic analysis reveals that the complex is a mononuclear complex. The Cu(II) atom is four-coordinated by the phenolate O atoms and imine N atoms fromtwo oxime-type ligands, in a square-planar geometry in which the dihedral angle of two coordination plane (Cu1N1O1 and Cu1N#1O#1) is 0°. The crystal packing of the Cu(II) complex shows that a notable feature of this structure resides in the formation of a novel 3D supramolecular networks through intermolecular O-H...N, C-H...O, and C-H...π interactions. Copyright Taylor & Francis Group, LLC.

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Synthesis and Crystal Structure of a 3D Supramolecular
Copper(II) Complex With 1-(3-{[(E)-3-bromo-5-chloro-2-
hydroxybenzylidene]amino}phenyl) ethanone Oxime
Yin-Xia Sun a , Li Xu a , Tian-Hao Zhao a , Sen-Hua Liu a , Guo-Hua Liu a & Xu-Tao Dong a
a School of Chemical and Biological Engineering , Lanzhou Jiaotong University , Lanzhou ,
Gansu , P. R. China
Accepted author version posted online: 10 Dec 2012.Published online: 26 Feb 2013.
To cite this article: Yin-Xia Sun , Li Xu , Tian-Hao Zhao , Sen-Hua Liu , Guo-Hua Liu & Xu-Tao Dong (2013)
Synthesis and Crystal Structure of a 3D Supramolecular Copper(II) Complex With 1-(3-{[(E)-3-bromo-5-chloro-2-
hydroxybenzylidene]amino}phenyl) ethanone Oxime, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
Chemistry, 43:4, 509-513, DOI: 10.1080/15533174.2012.740756
To link to this article: http://dx.doi.org/10.1080/15533174.2012.740756
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:509–513, 2013
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.740756
Synthesis and Crystal Structure of a 3D Supramolecular
Copper(II) Complex With 1-(3-{[(E)-3-bromo-5-chloro-2-
hydroxybenzylidene]amino}phenyl)
ethanone Oxime
Yin-Xia Sun, Li Xu, Tian-Hao Zhao, Sen-Hua Liu, Guo-Hua Liu,
and Xu-Tao Dong
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou, Gansu,
P. R. China
understood.[6–9] An extensive effort has been made to prepare
A new Cu(II) complex, [Cu(L)2], has been synthesized via
the complexation of copper(II) acetate monohydrate with a
new oxime-type ligand (HL = 1-(3-{[(E)-3-bromo-5-chloro-2-
hydroxybenzylidene]amino}phenyl)ethanone oxime). X-ray crys-
tallographic analysis reveals that the complex is a mononuclear
complex. The Cu(II) atom is four-coordinated by the phenolate O
atoms and imine N atoms from two oxime-type ligands, in a square-
planar geometry in which the dihedral angle of two coordination
plane (Cu1N1O1 and Cu1N#1O#1) is 0◦. The crystal packing of
the Cu(II) complex shows that a notable feature of this struc-
ture resides in the formation of a novel 3D supramolecular net-
works through intermolecular O–H···N, C–H···O, and C–H···π
interactions.
and characterize a variety of copper(II) coordination complexes
in an attempt to model the physical and chemical behavior
of copper-containing enzymes.[10] A kind of oxime-type
ligand can be obtained by the reaction of salicylaldehyde or
substituted salicylaldehyde with aminophenylethanone oxime.
A large number of the syntheses of such oxime-type ligands
and their metal complexes have been reported because of their
interesting structures and potential applications.[11,12] As an
extension of the work on the structural characterization of
such complexes,[13] the crystal structure of a new copper(II)
complex, [Cu(L)2], (HL = 1-(3-{[(E)-3-bromo-5-chloro-
2-hydroxybenzylidene]amino}phenyl)ethanone oxime), is
reported in this article.
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 supplemen-
tal file.
EXPERIMENTAL
Keywords oxime-type ligand, crystal structure, Cu(II) complex,
synthesis
Materials and Instruments
3-Bromo-5-chloro-2-hydroxybenzylidene from Alfa Aesar
(Tianjin, China) was used without further purification. 3-
Aminophenylethanone oxime was synthesized according to an
analogous method reported earlier.[13,14] The other reagents and
solvents were analytical grade reagents from Tianjin Chemical
Reagent Factory (China).
Elemental analyses for Cu was detected by an IRIS
ER/S·WP-1 ICP atomic emission spectrometer (TJA, USA).
C, H, and N analyses were carried out with a GmbH Vario
EL V3.00 automatic elemental analyzer (Elementar, Germany).
IR spectra were recorded on a VERTEX70 FT-IR spectropho-
tometer (Bruker, Germany), with samples prepared as KBr
(500–4000 cm−1) and CsI (100–500 cm−1) pellets. X-ray sin-
gle crystal structure was determined on a Bruker Smart APEX
CCD area detector (Germany). Melting points were obtained
by use of an X4 microscopic melting point apparatus made in
Beijing Taike Instrument Limited Company (China) and were
uncorrected.
INTRODUCTION
Oxime-type ligands and their metal complexes have been
playing an important part in the development of coordination
chemistry.[1] Metal ions with oxime-type ligands have been
widely investigated not only in coordination chemistry but also
in biological chemistry.[2–5] Copper(II) complexes appear that
the biological role of copper is primarily in redox reactions
and as a biological catalyst, although much remains to be
Received 7 April 2012; accepted 13 October 2012.
This work was supported by the Young Scholars Science Founda-
tion of Lanzhou Jiaotong University (2011007), which is gratefully
acknowledged.
Address correspondence to Yin-Xia Sun, School of Chemi-
cal and Biological Engineering, Lanzhou Jiaotong University,
Lanzhou, Gansu, 730070, P. R. China. E-mail: sun yinxia@163.com
509

510
Y.-X. SUN ET AL.
TABLE 1
Synthesis of the Ligand HL
Crystallographic data, data collection and structure refinement
for complex [Cu(L)2]
To an ethanol solution of 3-bromo-5-chlorin-2-hydroxy-
benzylidene (117.7 mg, 0.50 mmol) was added an ethanol so-
lution of 3-aminophenylethanone oxime (75.3 mg, 0.50 mmol).
The mixture solution was stirred at 328–333 K for 3–4 h. After
cooling to room temperature, the precipitate was filtered, and
washed successively with ethanol and n-hexane, respectively.
The product was dried under vacuum, and obtained orange red
microcrystal. Yield, 78.8 %. m.p. 449∼450 K. Anal. Calcd. for
C15H11ClBrN2O2 (%): C 49.01; H 3.29; N 7.62. Found (%): C
49.03; H 3.32; N 7.66.
Empirical formula
C30H22Br2Cl2CuN4O4
Formula weight
T/K
796.78
298(2)
Wavelength/Å
Crystal system
Space group
a/(Å)
0.71073
Monoclinic
P2(1)/n
11.9021(12)
11.0255(8)
12.4099(13)
90.00
113.4400(10)
90.00
b/(Å)
Synthesis of Copper(II) Complex
c/(Å)
A solution of copper(II) acetate monohydrate (2.1 mg,
0.010 mmol) in methanol (3.5 ml) was added dropwise to a
solution of HL (7.4 mg, 0.020 mmol) in methanol (2.5 ml)
at room temperature. The color of the mixing solution turned
brown immediately, and then continued to stirring for 0.5 h at
room temperature. The mixture solution was filtered and the
filtrate was allowed to stand at room temperature for about
four weeks, the solvent was partially evaporated and obtained
several brown block-like single crystals suitable for X-ray crys-
tallographic analysis. Anal. Calcd. for C30H22CuCl2Br2N4O4
([Cu(L)2]) (%): C 45.22; H 2.78; N 7.03; Cu 7.98. Found: C
45.24; H 2.75; N 6.98; Cu 8.03.
α/(◦)
β/(◦)
γ /(◦)
V/(Å3)
1494.1(2)
Z
2
Dc/(Mg · m−3
)
1.771
Absorption correction
F (000)
Semiempirical from equivalents
790.0
Crystal size/mm
θ Range for data
collection/(◦)
0.36 × 0.26 × 0.10
2.572–27.103
Index ranges
–14 ≤ h ≤ 7, –13 ≤ k ≤ 12, –14 ≤
l ≤ 14
Crystal Structure Determination
Completeness to θ =
25.01(%)
99.7
The X-ray diffraction measurement for the complex was
performed on Bruker Smart Apex CCD diffractometer (Ger-
many) with graphite-monochromated Mo Kα radiation (λ =
0.71073 Å) at 298(2) K. Empirical absorption correction was
applied to the data using SADABS program.[15] The structure
was solved by direct methods and refined by full-matrix least-
squares method on F2 using the SHELXL program.[16] All non-
hydrogen atoms were refined anisotropically. All the hydrogen
atoms were generated geometrically and refined isotropically
using the riding model. Details of the crystal parameters, data
collection and refinements for the complex are summarized in
Table 1.
Reflections collected
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
7659
2622 [R(int) = 0.0576]
Full-matrix least-squares on F2
2622/0/197
1.048
R1 = 0.0405, wR2 = 0.1051
[I > 2σ(I)]
R indices (all data)
R1 = 0.0553, wR2 = 0.1116
(ꢀρ)max/(e·Å−3
)
0.766
(ꢀρ)min/(e·Å−3
)
–0.887
RESULTS AND DISCUSSION
Crystal Structure of [Cu(L)2]
Cu atom (Table 2) are typical and comparable to the correspond-
ing values observed in other Cu(II) complexes with oxime-type
The crystal structure and atom numbering of the Cu(II) com- ligands.[17,18] The two oxime-type ligands are coordinated in a
plex, [Cu(L)2], is shown in Figure 1. Selected bond lengths and trans fashion. This is the same as the series mononuclear Cu(II)
bond angles are listed in Table 2. X-ray crystallographic anal- complexes our previously reported, in which the ligands are in
ysis of [Cu(L)2] reveals formation of a mononuclear structure. a trans arrangement.[19,20] The dihedral angle between the coor-
The Cu(II) complex crystallizes in the monoclinic system, space dination plane of O1-Cu1-N1 and that of O#1-Cu1-N#1 is 0◦.
group P2(1)/n, and Z = 2. The complex consists of one Cu(II)
The hydrogen bond data are summarized in Table 3. As
atom, two bidentate L− units, as expected from the analyti- illustrated in Figure 2, each oxime nitrogen atom N2 of the
cal data. In asymmetric molecule unit of the title complex, the two ligand molecules is hydrogen-bonded to the –O2H2 group
Cu(II) center is tetra-coordinated by the phenolate O atoms and of the oxime group from the other neighboring molecule re-
imine N atoms from two oxime-type ligands, in a square-planar sulted in the formation of a classical six-member ring. Syn-
geometry. The coordinate bond lengths and angles around the chronously, four weak intermolecular C11-H11···Cl1 hydrogen

SYNTHESIS AND STRUCTURE OF A COPPER(II) COMPLEX
511
TABLE 2
TABLE 3
Selected bond distances (Å) and bond angles (◦) for the Cu(II)
complex
Hydrogen bonding distances (Å) and bond angles (◦) for the
Cu(II) complex
Cu(1)-O(1) #1
Cu(1)-N(1) #1
O(1)#1-Cu(1)-O(1)
O(1)#1-Cu(1)-N(1)
O(1)-Cu(1)-N(1)
O(1)#1-Cu(1)-N(1)#1 91.4(1)
O(1)-Cu(1)-N(1)#1 88.6(1)
1.904(2) Cu(1)-O(1)
1.993(3) Cu(1)-N(1)
1.904(2)
1.993(3)
D-H···A
O2–H2···N2
C11-H11···Cl1
C7-H7···O1
d(D–H)
d(H···A)
2.108
2.941
2.651
d(D···A)
2.817(1)
3.645(2)
3.565(3)
∠ DHA
180.00
N(1)-Cu(1)-N(1)#1 180.0
0.819
0.930
0.930
144.87
133.58
167.81
88.6(1)
91.4(1)
C(1)-N(1)-Cu(1)
C(8)-N(1)-Cu(1)
C(3)-O(1)-Cu(1)
124.1(3)
123.7(2)
129.3(2)
bonds are formed between the chlorine atoms (Cl1) and the
–C11H11 group of the L− unit. Thus, each Cu(II) complex
molecule linked four other adjacent molecules into an infinite
two-dimensional supramolecular planar structure along the bc
plane (Figure 2). Furthermore, this linkage is further stabilized
by four C7-H7···O1 hydrogen bonds between the phenolate oxy-
gen (O1) atom and the –C7H7 group of benzene ring and four
C15-H15···πcentroid(C2-C7) interactions between the -CH groups
of the methyl groups and the benzene rings of L− unit to form
the other 2D infinite supramolecular planar structure along the
ab plane (Figure 3). The crystal packing of the Cu(II) complex
shows that a notable feature of this structure resides in the forma-
tion of a novel 3D supramolecular networks through intermolec-
ular O–H···N, C–H···O, and C–H···π interactions (Figure 4).
FT-IR Spectra of [Cu(L)2]
The FT-IR spectra of HL and its corresponding Cu(II) com-
plex in the 400–4000 cm−1 region is given in Figure 5. The
free ligand HL exhibits characteristic C N stretching bands
at 1608 cm−1, while that of C N of the Cu(II) complex was
observed in the 1618 cm−1. The C N stretching frequency is
FIG. 1. The molecular structure and atomic numbering scheme in the Cu(II)
complex, showing 30% probability displacement ellipsoids.
FIG. 2. View of an infinite 2D supramolecular network of the Cu(II) complex on the bc plane (hydrogen atoms, except those forming hydrogen bonds, are omitted
for clarity) (color figure available online).

512
Y.-X. SUN ET AL.
FIG. 5. FT-IR spectra of the ligand and its Cu(II) complex.
FIG. 3. View of an infinite 2D supramolecular network of the Cu(II) complex
on the ab plane (hydrogen atoms, except those forming hydrogen bonds, are
omitted for clarity) (color figure available online).
were attributed to aromatic C C vibrations. Upon coordination
these bands shift to lower frequencies for the Cu(II) complex.
In addition, the O-H stretching frequency of the free HL ligand
appears at 3287 and 3239 cm−1. The out-of-plane bending vibra-
tion of phenolic alcohol in HL at 1222 cm−1, which disappears
in the complex, indicating the oxygen in the phenolic alcohol
of the complex has been deprotonated and coordinated to the
Cu(II) atom. Meanwhile, infrared spectrum of Cu(II) complex
shows the expected strong absorption band due to υ(O–H) at
ca. 3415 cm−1, which is the evidence for the existence of oxime
group.
The far-infrared spectrum of the Cu(II) complex was also
obtained in the region 100–500 cm−1 in order to identify fre-
quencies due to the Cu-O and Cu-N bonds. The FT-IR spectrum
of the complex showed υ(Cu-N) and υ(Cu-O) vibration absorp-
tion frequencies at 498 cm−1 and 441 cm−1, respectively.[20]
shifted to higher frequency by ca. 10 cm−1 upon complexa-
tion, indicating the behavior between the free ligand and the
corresponding Cu(II) ion resulting in strengthening the force
constant of C N bond. The Ar–O stretching frequencies ap-
pear as a strong band in the 1161 cm−1 in the free ligand, and
the toward high wave number of the Ar–O absorption shift ca.
2 cm−1 indicating that Cu–O bonds are formed between the
Cu(II) atom and the oxygen atoms of the phenolic groups.[12,19]
The N–O stretching frequencies of the oxime group in free
ligand and the complex appear as a strong band in the 874 and
887 cm−1, indicating that the oxime N atoms do not involve in
coordination. In the 1438–1514 cm−1 region, the observed bands
FIG. 4. View of a self-assembling 3D supramolecular structure of the Cu(II) complex (hydrogen atoms, except those forming hydrogen bonds, are omitted for
clarity) (color figure available online).

SYNTHESIS AND STRUCTURE OF A COPPER(II) COMPLEX
513
SUPPLEMENTARY MATERIALS
benzyldithiocarbazate and the X-ray crystal structure of bis[S-benzyl-β-
N-(5-methyl-2-furylmethylene)dithiocarbazato]cadmium(II). Polyhedron
2002, 21, 2547–2554.
9. Musie, G.T.; Li, X.; Powell, D.R. Synthesis, crystal structure and redox
properties of bis-imidazolyl-containing copper(II) complexes. Inorg. Chem.
Acta 2003, 348, 69–74.
10. Reddy, P.A. N.; Datta, R.; Chakravarty, A.R. Synthesis, X-ray structure
and catalytic properties of a copper(II) Schiff base complex modeling the
activity of the CuB site of dopamine β-hydroxylase. Inorg. Chem. Commun.
2000, 3, 322–324.
11. Akine, S.; Taniguchi, T.; Dong, W.K.; Nabeshima, T. Oxime-based salen-
type tetradentate ligands with high stability against imine metathesis reac-
tion. J. Org. Chem. 2005, 70, 704–1711.
Crystallographic data has been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary pub-
lication, No. CCDC 859479 for the Cu(II) complex. Copies
of the data can be obtained free of charge on application
to CCDC, 12 Union Road, Cambridge CB21EZ, UK (Tele-
phone: (44) 01223 762910; Fax: +44-1223-336033; E-mail:
deposit@ccdc.cam.ac.uk). These data can be also obtained free
of charge at www.ccdc.cam.ac.uk/conts/retrieving.htm.
12. Dong, W.K.; Duan, J.G.; Guan, Y.H.; Shi, J.Y.; Zhao, C.Y. Synthesis, crystal
structure and spectroscopic behaviors of Co(II) and Cu(II) complexes with
Salen-type bisoxime ligands. Inorg. Chim. Acta 2009, 362, 1129–1134.
13. Dong, W.K.; Yao, J.; Sun, Y.X.; Li, L.; Wu, J.C. Two copper(II) complexes
with mono-oxime chelating ligands: synthesis, crystal structure, and sub-
stituent effect. Synth. React. Inorg. Met-Org. Nano-Met. Chem. 2010, 40,
521–528.
14. Dong, W.K.; Shi, J.Y.; Zhong, J.K.; Tian, Y.Q.; Duan, J.G. Synthesis, crystal
structure and Infrared spectral analysis for a novel trinuclear nickel(II)
cluster. Chin. J. Inorg. Chem. 2008, 24, 10–14.
15. Sheldrick, G.M. SADABS, University of Go¨ttingen, Germany, 1996.
16. Sheldrick, G.M. SHELXTL 5.10 for Windows NT, Structure Determina-
tion Software; Bruker Analytical, X-Ray Systems, Inc., Madison, WI,
1997.
17. Dong, W.K.; He, X.N.; Yan, H.B.; Lv, Z.W.; Chen, X.; Zhao, C.Y.; Tang,
X.L. Synthesis, structural characterization and solvent effect of copper(II)
complexes with a variational multidentate Salen-type ligand with bisoxime
groups. Polyhedron 2009, 28, 1419–1428.
REFERENCES
1. Adhikary, C.; Sen, R.; Bocelli, G.; Cantoni, A.; Solzi, M.; Chaudhuri,
S.; Koner, S. Tridentate (NNO) Schiff-base copper(II) complex: synthe-
sis, crystal structure, and magnetic study. J. Coord. Chem. 2009, 62,
3573–3582.
2. Rajasekar, M.; Sreedaran, S.; Prabu, R.; Narayanan, V.; Jegadeesh, R.; Raa-
man, N.; Kalilur Rahiman, A. Synthesis, characterization, and antimicro-
bial activities of nickel(II) and copper(II) Schiff-base complexes. J. Coord.
Chem. 2010, 63, 136–146.
3. Qin, D.D.; Yang, Z.Y.; Zhang, F.H.; Du, B.; Wang, P.; Li, T.R. Evaluation
of the antioxidant, DNA interaction and tumor cell cytotoxicity activities
of copper(II) complexes with Paeonol Schiff-base. Inorg. Chem. Commun.
2010, 13, 727–729.
4. Dong, W.K.; Ding, Y.J. Growth and structural characterization of
[ZnL(DMSO)]. Cryst. Res. Technol. 2007, 43, 321–326.
5. Xiao, J.M.; Zhang, W. In situ synthesis and dielectric properties of cop-
per(II) and nickel(II) chiral Schiff base complexes. Inorg. Chem. Commun.
2009, 12, 1175–1178.
18. Kulkarni, V.H.; Patil, B.R.; Prabhakar, B.K. IR and Mo¨ssbauer studies of
Sn(IV) complexes with branched tetradentates containing N and O donor
centres. J. Inorg. Nucl. Chem. 1981, 43, 17–21.
19. Dong, W.K.; Feng, J.H.; Wang, L.; Xu, L.; Zhao, L.; Yang, X.Q.
Synthesis and structural characterization of a novel tetranuclear Cu(II)
complex:[Cu4L2(pic)4(H2O)2]·2H2O. Transition Met. Chem. 2007, 32,
1101–1105.
6. Collinson, S.R.; Fenton, D.E. Metal complexes of bibrachial Schiff base
macrocycles. Coord. Chem. Rev. 1996, 148, 19–40.
7. Hossain, M.E.; Alam, M.N.; Begum, J.; Akbar, A.M.; Nazimuddin, M.;
Smith, F.E.; Hynes, R.C. The preparation, characterization, crystal struc-
ture and biological activities of some copper(II) complexes of the 2-
benzoylpyridine Schiff bases of S-methyl- and S-benzyldithiocarbazate.
Inorg. Chem. Acta 1996, 249, 207–213.
8. Tarafder, M.T. H.; Jin, K.T.; Crouse, K.A.; Ali, A.M.; Yamin, B.M.;
Fun, H.K. Coordination chemistry and bioactivity of Ni2+, Cu2+, Cd2+
and Zn2+ complexes containing bidentate Schiff bases derived from S-
20. Dong, W.K.; Wang, Y.; Wu, J.C.; Zhang, S.T. Bis{(E)-2-[(2-chloro-
3-pyridyl)iminomethyl]-6-methoxyphenolato-κ2N,O1}copper(II).
Cryst. 2011, E67, m91.
Acta