Synthesis and crystal structure of a rarely seen terephthalato-bridged dinuclear copper(II) complex [Cu2(CMP)2(TPA)] ·[Cu2(CMP)2(MeOH)2(TPA)]·2H 2O

Article abstract of DOI:10.1080/15533174.2012.753619

A rarely seen terephthalato-bridged dinuclear copper(II) complex, [Cu ₂(CMP)₂(TPA)]·[Cu₂(CMP) ₂(MeOH)₂(TPA)]·2H₂O (CMP = 4-chloro-2-[(2-isopropylaminoethylimino)methyl]pheno-late, TPA = ter

Full text of DOI:10.1080/15533174.2012.753619

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1025–1028, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.753619
Synthesis and Crystal Structure of a Rarely Seen
Terephthalato-Bridged Dinuclear Copper(II) Complex
[
Cu (CMP) (TPA)]·[Cu (CMP) (MeOH) (TPA)]·2H O
2
2
2
2
2
2
1
2
1
2
Shao-Song Qian, Dong-Mei Xian, Yue-Hu Chen, Zhong-Lu You,
1
and Hai-Liang Zhu
1
School of Life Sciences, Shandong University of Technology, ZiBo, P. R. China
2
Department of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, P. R. China
a rarely seen terephthalato-bridged dinuclear copper(II) com-
A rarely seen terephthalato-bridged dinuclear copper(II) plex, [Cu2(CMP)2(TPA)]·[Cu2(CMP)2(MeOH)2(TPA)]·2H2O
complex, [Cu
2
(CMP)
2
(TPA)]·[Cu
2
(CMP)
2
(MeOH)
2
(TPA)]·2H
2
O
(CMP = 4-chloro-2-[(2-isopropylaminoethylimino)methyl]ph-
enolate, TPA = terephthalate), has been successfully prepared
and characterized.
(
CMP = 4-chloro-2-[(2-isopropylaminoethylimino)methyl]pheno-
late, TPA = terephthalate), has been prepared and characterized
by elemental analysis, infrared spectrum, and single crystal X-ray
determination. The complex crystallizes in the triclinic space group
P–1, with a = 9.741(1) Å, b = 11.248(2) Å, c = 17.659(2) Å, α =
EXPERIMENTAL
◦
◦
◦
3
9
1
5.915(2) , β = 90.656(2) , γ = 111.747(2) , V = 1785.0(4) Å , Z =
Materials and Measurements
, GOOF = 1.033, R = 0.0432, and wR = 0.1109. The asymmetric
1
2
unit of the complex contains two centrosymmetric terephthalato-
bridged dinuclear copper(II) molecules and two water molecules
of crystallization. The Cu atoms in one molecule are in square pla-
nar coordination, and in the other one are in square pyramidal
coordination.
5-Chlorosalicylaldehyde and N-isopropylethane-1,2-dia
mine were purchased from Lancaster (England). All other chem-
icals (reagent grade) were commercially available and used
without further purification. Elemental analyses for C, H, and
N were performed on a Perkin-Elmer 240C elemental analyzer
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.
(
Nanjing University, China). Infrared spectra were recorded on
a Nicolet AVATAR 360 spectrophotometer (Liaoning Normal
University, China) as KBr pellets.
Synthesis of HCMP
Keywords copper complex, crystal structure, dinuclear complex,
HCMP was prepared by condensation of equimolar quan-
tities of 5-chlorosalicylaldehyde with N-isopropylethane-1,2-
diamine in methanol at room temperature. Yield: 90%. Found:
C, 59.7; H, 7.1; N, 11.7. Anal. Calcd. (%) for C12H17ClN2O: C,
Schiff base, X-ray crystallography
INTRODUCTION
59.9; H, 7.1; N, 11.6.
Polynuclear complexes have been widely investigated due
to their versatile molecular structures and interesting function-
Synthesis of [Cu2(CMP)2(TPA)]·[Cu2(CMP)2
alities.[
1–3]
The main strategy for designing polynuclear com-
(MeOH)2(TPA)]·2H2O
plexes is to use suitable bridging ligands such as azide, thio-
[
4–7]
Terephthalic acid (0.1 mmol, 16.6 mg) and LiOH (0.2 mmol,
cyanate, cyanide, and so on.
Among polynuclear complexes,
4.8 mg) were mixed and stirred in distilled water (3 mL) for
those containing Cu atoms usually possess interesting magnetic
properties.[
8–10]
30 min. In addition, the Schiff base ligand (0.2 mmol, 48.1 mg)
and copper perchlorate (0.2 mmol, 75.0 mg) were mixed and
stirred in methanol (15 mL) for 30 min. Then, two mixtures
were combined together, and further stirred for 2 h at room
temperature, and filtered. Upon keeping the filtrate in air for a
few days, blue block-shaped crystals of the complex, suitable for
X-ray crystal structure determination, were formed. The crystals
were isolated by filtration, washed with methanol, and dried in a
vacuum desiccator containing anhydrous CaCl2. Yield 37% on
the basis of HCMP. Found: C, 48.5; H, 5.3; N, 6.7. Anal. Calcd.
(%) for C H Cl Cu N O : C, 48.3; H, 5.2; N, 6.8.
Multicarboxylate anions have also been exten-
sively used to prepare polynuclear complexes. However, to the
best of our knowledge, only seven Schiff base copper(II) com-
plexes with multicarboxylate bridges have been reported.[11–17]
As an extension of work on such complexes, in this study,
Received 16 May 2012; accepted 24 November 2012.
Address correspondence to Hai-Liang Zhu, School of Life Sciences,
Shandong University of Technology, ZiBo 255049, P. R. China. E-mail:
hailiang zhu@163.com
66
84
4
4
8
16
1025

1026
S.-S. QIAN ET AL.
TABLE 1
Crystallographic data and refinement parameters
for the complex
TABLE 2
◦
Selected bond distances (Å) and angles ( ) for the complex
Bond distances
Cu1–O1
Cu1–N1
Cu1–O4
Cu2–O5
Cu2–N3
Bond angles
O1–Cu1–O2
O2–Cu1–N1
O2–Cu1–N2
O5–Cu2–N3
N3–Cu2–O6
N3–Cu2–N4
O1–Cu1–O4
N1–Cu1–O4
1.932(2)
1.944(2)
2.315(2)
1.912(2)
1.943(2)
Cu1–O2
Cu1–N2
1.9353(19)
2.051(3)
Molecular formula
Formula moiety
C66H84Cl4Cu4N8O16
C34H44Cl2Cu2N4O8·C32H36
Cl2Cu2N4O6·2H2O
1641.4
Cu2–O6
Cu2–N4
2.021(3)
2.034(3)
Molecular weight
Temperature (K)
Crystal shape/color
Crystal dimensions (mm)
Crystal system
Space group
a (Å)
298(2)
Block/blue
0.27 × 0.23 × 0.23
Triclinic
P–1
9.741(1)
11.248(2)
17.659(2)
95.915(2)
90.656(2)
111.747(2)
1785.0(4)
1
1.527
1.396
91.7(1)
171.3(1)
91.7(1)
91.9(1)
177.6(1)
84.2(1)
93.7(1)
99.8(1)
O1–Cu1–N1
O1–Cu1–N2
N1–Cu1–N2
O5–Cu2–O6
O5–Cu2–N4
O6–Cu2–N4
O2–Cu1–O4
N2–Cu1–O4
92.4(1)
176.5(1)
84.4(1)
88.4(1)
166.2(1)
96.0(1)
87.6(1)
85.6(1)
b (Å)
c (Å)
◦
α ( )
◦
β ( )
◦
γ ( )
Volume (Å )
X-Ray Crystallography
Diffraction intensities for the complex were collected at
98(2) K using a Bruker D8 VENTURE PHOTON diffractome-
ter (Shandong University of Technology, China) with MoKα
radiation (λ = 0.71073 Å). Collected data were reduced us-
ing SAINT,[ and multiscan absorption corrections were per-
formed using SADABS.[ Structure of the complex was solved
3
Z
2
−
3
dcalc (g cm )
Absorption coefficient
−
1
(
mm )
18]
F(000)
θ range ( )
848
19]
◦
1.96/27.00
–11/12, –13/14, –22/11
Multi-scan
0.7043
0.4395
7562/462
6162
2
by direct method and refined against F by full-matrix least-
Range/indices (h, k, l)
Absorption correction
Tmin
squares method using SHELXTL.[ All of the non-hydrogen
atoms were refined anisotropically. Water and amino H atoms in
the complex were located in a difference Fourier map and refined
isotropically, with O–H, N–H, and H···H distances restrained to
20]
Tmax
Reflections/parameters
Independent reflections
Restraints
0
.85(1), 0.90(1), and 1.37(2) Å, respectively. All other H atoms
were placed in idealized positions and constrained to ride on
their parent atoms. Crystallographic data for the complex are
summarized in Table 1. Selected bond lengths and angles are
given in Table 2.
6
2
Goodness of fit on F
1.033
0.0432, 0.1109
0.0545, 0.1198
a
R1, wR2 [I ≥ 2σ(I)]
a
R1, wR2 (all data)
ꢀ
ꢀ
ꢀ
ꢀ
aR
2
2 2
2 2 1/2
1
=
||Fo| – |Fc||/ |Fo|, wR
2
2
= [ w(Fo – Fc ) / w(Fo ) ]
,
RESULTS AND DISCUSSION
2
2
2
2
2
2
−1
w = [σ Fo + (0.0561(Fo + 2Fc )/3) + 2.1709(Fo + 2Fc )/3]
.
Crystal Structure Description of the Complex
The asymmetric unit of the compound contains two
centrosymmetric terephthalato-bridged dinuclear copper(II)
FIG. 1. The Cu1 complex molecule of the complex at 30% probability displacement. Unlabeled atoms are at the symmetry position 2 – x, – y, – z.

A RARELY SEEN DINUCLEAR COPPER(II) COMPLEX
1027
FIG. 2. The Cu2 complex molecule of the complex at 30% probability displacement. Unlabeled atoms are at the symmetry position 1 – x, 1 – y, 2 – z.
molecules (Figures 1 and 2), and two water molecules of crystal- bond values are typical and comparable with those observed
lization. For the Cu1 molecule, each Cu atom is in a square pyra- in other similar copper(II) complexes with Schiff bases.[
midal coordination, with the phenolic O, imino N, and amino In line with the amphimonodentate coordination mode of the
N atoms of the Schiff base ligand, and with one terephthalate O carboxylate groups is the marked difference of 0.042(2) Å for
atom defining the basal plane, and with one methanol O atom O2-C13-O3 and 0.007(2) Å for O6-C30-O7 between the two C-
occupying the apical position. The distortion of the square pyra- O distances, implying a partial double bond character of C13-O3
mid can be observed from the coordinate bond angles among the and C30-O7 bonds. In the terephthalate groups, the dihedral an-
11,16,17]
◦
apical and basal donor atoms, ranging from 85.6(1) to 99.8(1) . gles between the benzene rings and the planes defined by the
◦
◦
The apical bond is much longer than the basal bonds. Cu1 atom carboxylate groups are 3.6(3) for Cu1 and 10.9(3) for Cu2.
deviates from the least-squares plane defined by the four basal The molecular packing structure of the complex is shown in
donor atoms by 0.056(2) Å toward the apical donor atom. The Figure 3. The crystal of the complex is linked by intermolecular
intramolecular Cu···Cu separation is 11.0(2) Å. For the Cu2 O–H···O and N–H···O hydrogen bonds.
molecule, each Cu atom is four-coordinated by the phenolic O,
iminoN, andaminoN atomsoftheSchiffbaseligand, andbyone IR Spectra
terephthalate O atom, forming a square planar geometry. Cu2
atom deviates from the least-squares plane defined by the four
donor atoms by 0.092(2) Å. The intramolecular Cu···Cu sepa-
ration is 10.9(2) Å. Detailed comparison of the two molecules
indicates that the coordinate bond lengths in Cu1 molecule are
a little longer than those in Cu2 molecule. All the coordinate
The characteristic feature of the infrared spectrum of the
complex is the positions of νas(COO) and νs(COO) bands
−
l
at 1593 and 1392 cm , respectively. Their difference, ꢀ =
−1
2
01 cm , is characteristic of the monodentate coordination
mode of the terephthalate ligands. The strong absorption band
of the C N bonds in the complex is at 1640 cm . The O–H
[
21]
−1
FIG. 3. Molecular packing structure of the complex, viewed along the a-axis. Hydrogen bonds are drawn as dashed lines.

1028
S.-S. QIAN ET AL.
−1
and N–H vibrations are observed at 3436, 3331, and 3168 cm .
The weak bands located at the low numbers may be assigned to
the ν(Cu–O) and ν(Cu–N).
7. Cern a´ k, J.; Chomic, J.; Massa, W. Cu2(dien)2Ag5(CN)9 containing the
n+
one-dimensional polymeric cation [Cu(dien)Ag(CN)2]n and the unusual
-
[
Ag2(CN)3] anion (dien is diethylenetriamine). Acta Crystallogr. 2002,
C58, m490–m493.
8
. Rigamonti, L.; Forni, A.; Pievo, R.; Reedijk, J.; Pasini, A. Synthesis, crystal
structures and magnetic properties of dinuclear copper(II) compounds with
NNO tridentate Schiff base ligands and bridging aliphatic diamine and
aromatic diimine linkers. Dalton Trans. 2011, 40, 3381–3393.
CONCLUSIONS
A rarely seen terephthalato-bridged dinuclear copper(II)
complex derived from 4-chloro-2-[(2-isopropylaminoethylim
ino)methyl]phenol and terephthalic acid was prepared and
characterized. The single-crystal structure of the complex was
determined. The synthesis of the complex indicates that the
terephthalate anion is an interesting bridging group for the con-
struction of polynuclear complexes. The present copper com-
plex may possess interesting magnetic property, which deserves
further investigation.
9. Talukder, P.; Shit, S.; Sasmal, A.; Batten, S.R.; Moubaraki, B.; Mur-
ray, K.S.; Mitra, S. An antiferromagnetically coupled hexanuclear cop-
per(II) Schiff base complex containing phenoxo and dicyanamido bridges:
structural aspects and magnetic properties. Polyhedron 2011, 30, 1767–
1
773.
1
0. Sadhukhan, D.; Ray, A.; Butcher, R.J.; Garcia, C.J. G.; Dede, B. Magnetic
and catalytic properties of a new copper(II)-Schiff base 2D coordination
polymer formed by connected helical chains. Inorg. Chim. Acta 2011, 376,
2
45–254.
1
1. Xanthopoulos, C.E.; Sigalas, M.P.; Katsoulos, G.A.; Tsipis, C.A.;
Terzis, A.; Mentzafos, M.; Hountas, A. Crystal and molecular-
structure and magnetism of (μ-terephthalato)bis[(n-(2-(diethylamino)
ethyl)salicylidenaminato)copper(II)]-water-methanol. Inorg. Chem. 1993,
SUPPLEMENTARY MATERIALS
CCDC-867565 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
at http://www.ccdc.cam.ac.uk/const/retrieving.html or from the
Cambridge Crystallographic Data Centre (CCDC), 12 Union
Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033 or
e-mail: deposit@ccdc.cam.ac.uk.
3
2, 5433–5436.
1
1
1
2. Branzea, D.G.; Guerri, A.; Fabelo, O.; Ruiz-Perez, C.; Chamoreau, L.-M.;
Sangregorio, C.; Caneschi, A.; Andruh, M. Heterobinuclear complexes as
tectons in designing coordination polymers. Cryst. Growth Des. 2008, 8,
9
41–949.
3. Dhara, K.; Roy, P.; Ratha, J.; Manassero, M.; Banerjee, P. Synthesis,
crystal structure, magnetic property and DNA cleavage activity of a new
tereplithalate-bridged tetranuclear copper(II) complex. Polyhedron 2007,
2
6, 4509–4517.
REFERENCES
4. Gheorghe, R.; Cucos, P.; Andruh, M.; Costes, J.-P.; Donnadieu, B.; Shova,
S. Oligonuclear 3d-4f complexes as tectons in designing supramolecular
solid-state architectures: Impact of the nature of linkers on the structural
diversity. Chem. Eur. J. 2006, 12, 187–203.
2+
1
. Wang, X.-Y.; Li, B.-L.; Zhu, X.; Gao, S. Extended networks of Co and
2+
−
−
Mn bridged by NCS /N3 anions and flexible long spacers: Synthe-
ses, structures, and magnetic properties. Eur. J. Inorg. Chem. 2005, 16,
3
277–3286.
. Brooker, S.; Plieger, P.G.; Moubaraki, B.; Murray, K.S. [CoII
L(NCS)2(SCN)2]: the first cobalt complex to exhibit both exchange cou-
15. Pascu, M.; Lloret, F.; Avarvari, N.; Julve, M.; Andruh, M. Ferromagnetic
II
II
2
2
coupling through spin polarization in the hexanuclear [Mn 3Cu 3] com-
plex. Inorg. Chem. 2004, 43, 5189–5191.
pling and spin crossover effects. Angew. Chem. Int. Ed. 1999, 38, 408–410. 16. Xanthopoulos, C.E.; Hadjikostas, C.C.; Katsoulos, G.A.; Terzis,
3
. Melaiye, A.; Sun, Z.; Hindi, K.; Milsted, A.; Ely, D.; Reneker, D.H.; Tessier,
C.A.; Youngs, W.J. Silver(I)-imidazole cyclophane gem-diol complexes
encapsulated by electrospun tecophilic nanofibers: formation of nanosil-
ver particles and antimicrobial activity. J. Am. Chem. Soc. 2005, 127,
A.; Sigalas, M.P. Molecular structure and magnetic properties
of the binuclear phthalato-bridged species bis[(N-(2-(diethylamino)
ethyl)salicylidenaminato)copper(II)] trihydrate. J. Coord. Chem. 2002, 55,
563–572.
2
285–2291.
17. Swamy, G.Y. S. K.; Ravikumar, K.; Chandramohan, K.; Lakshmi, N.V.
The crystal and molecular structure of (μ-terephthlato) bis[(N-salicylidene-
Nprime;-(2-hydroxyethyl)ethylenediamine) copper(II)]. Cryst. Res. Tech-
nol. 2001, 36, 1273–1279.
4
. Dey, S.K.; Mondal, N.; El Fallah, M.S.; Vicente, R.; Escuer, A.; Solans, X.;
Font-Bard ´ı a, M.; Matsushita, T.; Gramlich, V.; Mitra, S. Crystal structure
and magnetic interactions in nickel(II) dibridged complexes formed by two
azide groups or by both phenolate oxygen-azide, -thiocyanate, -carboxylate, 18. Bruker. SMART and SAINT. Bruker AXS Inc., Madison, WI, 2002.
or -cyanate groups. Inorg. Chem. 2004, 43, 2427–2434.
19. Sheldrick, G.M. SADABS. Program for Empirical Absorption Correction
5. Sun, H.-L.; Ma, B.-Q.; Gao, S.; Batten, S.R. A novel acentric three-
of Area Detector; University of G o¨ ttingen, Germany, 1996.
dimensional network with complicated topology. Cryst. Growth Des. 2006, 20. Sheldrick, G.M. SHELXTL V5.1 Software Reference Manual, Bruker AXS,
6
, 1261–1263.
. Woodward, J.D.; Backov, R.; Abboud, K.A.; Talham, D.R. [Ni(terpy)
H2O)]-trans-[Ni(μ-CN)2(CN)2]n, a one-dimensional linear tetracbreak;
yanonickelate chain. Acta Crystallogr. 2001, C57, 1027–1029.
Inc., Madison, Wisconsin, WI, 1997.
6
21. Deacon, G.B.; Phillips, R.J. Relationships between the carbon-oxygen
stretching frequencies of carboxylato complexes and the type of carboxylate
coordination. Coord. Chem. Rev. 1980, 33, 227–250.
(

Copyright of Synthesis & Reactivity in Inorganic, Metal-Organic, & Nano-Metal Chemistry is the property of
Taylor & Francis Ltd and its content may not be copied or emailed to multiple sites or posted to a listserv
without the copyright holder's express written permission. However, users may print, download, or email
articles for individual use.