Synthesis and crystal structures of one-dimensional chain copper(II) complexes of two phenol-containing schiff-base ligands

Article abstract of DOI:10.14233/ajchem.2013.14663

Two copper(II) complexes of the tridentate Schiff-base ligands (L ¹)^- and (L²)^-, [CuL1(μ-Br)] _∞ (1) and [CuL²(μ_1,3-N ₃)]_∞ (2), have been synthesized and cha

Full text of DOI:10.14233/ajchem.2013.14663

Asian Journal of Chemistry; Vol. 25, No. 14 (2013), 7867-7870
http://dx.doi.org/10.14233/ajchem.2013.14663
Synthesis and Crystal Structures of One-Dimensional Chain Copper(II)
Complexes of Two Phenol-Containing Schiff-Base Ligands
1,2
1,2, *
2
2
2
MIN ZHANG , RONG-QING LI
, ZAI-CHAO ZHANG , ZHENG-JING JIANG and CHANG-MEI WEI
1
2
School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, Ningxia Province, P.R. China
Jiangsu Key Laboratory for the Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal
University, Huai'an, Jiangsu Province, P.R. China
Corresponding author: Fax: +86 517 83525795; Tel: +86 517 83525790; E-mail: rongqingli333@yahoo.com
Received: 11 October 2012; Accepted: 22 July 2013)
*
(
AJC-13829
1
–
2
–
1
2
Two copper(II) complexes of the tridentate Schiff-base ligands (L ) and (L ) , [CuL (µ-Br)]
∞
(1) and [CuL (µ1,3-N
)]
3 ∞
(2), have been
1
–
2 –
synthesized and characterized. The ligands [(L ) and (L ) are the deprotonated forms of 2-[(2-morpholin-4-ylethylimino)methyl]phenol
HL ) and 2-[(2-piperidin-1-ylethylimino)methyl]phenol (HL ), respectively]. X-Ray structure determinations carried out on complexes
and 2 reveal that both complexes are mono(µ-bromo)-bridged (for 1) or mono(µ1,3-azido)-bridged (for 2) square pyramidal copper(II)
1
2
(
1
one-dimensional chain polymeric complexes.
Key Words: Schiff-base, Copper(II) complexes, Tridentate ligand, Phenol, Thermal analysis.
mono(µ1,3-azido)-bridged (for 2) square pyramidal copper(II)
INTRODUCTION
one-dimensional chain polymeric complexes.
Over the years much attention has been paid to the poly-
EXPERIMENTAL
nuclear metal complexes due to their potential applications in
1
, 2
3-6
the areas such as metalloenzyme models , catalysts ,
All chemicals and solvents were of reagent grade and were
7
-9
10-12
1
magnetic materials and photoelectronic devices .A lot of
different types of polynucleating ligands and their metal
used as received. H NMR spectra were recorded on a Bruker
AVANCE 400 MHz spectrometer with tetramethylsilane as
an internal reference. Infrared spectra were obtained on a
Nicolet Avatar 360 FT-IR spectrometer as pressed KBr discs.
Thermogravimetric measurements were carried out on a
NETZSCH STA 449F3 thermal analyzer from room tempe-
13-15
complexes have been reported . Of these ligands, the Schiff-
bases containing phenol units attracted particular attention.
This is because the phenol group has many useful electronic
and structural characteristics, such as the bridging capability
of the phenol oxygen atom and the easy fuctionalization and
-
1
rature to 1000 ºC in air with a heating rate of 10 ºC min .
16
1
2
1
great synthetic flexibility for the benzene ring present . Many
dinuclear and polynuclear complexes with phenol-containing
Schiff-base ligands have been reported, which exhibit inter-
Synthesis of ligands HL and HL : Ligands HL and
2
HL were synthesized by condensation of salicylaldehyde
(0.612 g, 5.0 mmol) with N-(2-aminoethyl)morpholine (0.650
g, 5.4 mmol) and N-(2-aminoethyl)piperidine (0.641 g, 5
mmol), respectively, in ethanol (30 mL) at room temperature.
After rotary evaporation of the solvent and drying in vacuo,
1
6-18
esting properties . For polynuclear complexes, their cata-
lytic, biological and magnetic properties usually rely on the
unsaturated coordination environments of the metal ions and
the distance between the adjacent metal ions. We to report
here the synthesis, crystal structures and properties of two new
1
2
HL was given as a yellow oil in 98 % yield and HL as an
1
9,20 1
orange oil in 97 % yield . H NMR data (CDCl , ppm): For
3
1
–
2
–
1
one-dimensional chain copper(II) complexes of (L ) and (L )
HL : δ = 2.56 (t, 4H), 2.72 (t, 2H), 3.75 (m, 6H), 6.90 (t, 1H),
1
2
1
–
in the forms of [CuL (µ-Br)]
and (L ) are the deprotonated forms of 2-[(2-morpholin-4-
ylethylimino)methyl]phenol (HL ) and 2-[(2-piperidin-1-
∞
(1) and [CuL (µ1,3-N
3
)]
∞
(2) [(L )
6.98 (d, 1H), 7.27 (m, 1H), 7.32 (m, 1H), 8.38 (s, 1H), 13.42
2
–
2
(s, 1H). For HL : δ = 1.46 (m, 2H), 1.62 (m, 4H), 2.50 (s, 4H),
1
2.68 (t, 2H), 6.88 (t, 1H), 6.97 (d, 1H), 7.30 (m, 2H), 8.37 (s,
2
ylethylimino)methyl]phenol (HL ), respectively]. X-Ray struc-
1H), 13.51 (s,1H).
Synthesis of [CuL (µ-Br)]
1
ture determinations carried out on complexes 1 and 2 reveal
that both complexes are mono(µ-bromo)-bridged (for 1) or
∞
(1): To a solution of ligand
1
HL (0.106 g, 0.45 mmol) in methanol (5 mL) was added

7
868 Zhang et al.
Asian J. Chem.
triethylamine (0.046 g, 0.45 mmol) in methanol (2 mL). To
this resulting solution was added dropwise a deep yellow
solution of copper(II) bromide (0.106 g, 0.45 mmol) in
methanol (2 mL), giving a green solution. The resulting solu-
tion was stirred overnight and then evaporated slowly for
TABLE-1
CRYSTALLOGRAPHIC DATA FOR 1 AND 2
1
2
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system
Space group
C H BrN O Cu
C H N O Cu
28 38 10 2 2
13 17
2
2
376.74
295(2) K
0.71073 Å
Monoclinic
P2(1)/c
a = 7.4413(15) Å
b = 22.370(5) Å
c = 8.6975(17) Å
β = 105.60(3)°
1394.5(5) Å
4, 1.794 Mg/m
673.76
296(2) K
0.71073 Å
Tetragonal
P4(3)2(1)2
5
days, and finally green crystals formed. The crystals were
collected by filtration, washed with methanol and dried in
vacuo (0.019 g, yield: 11 %). Single crystals suitable for
X-ray determination were obtained by vapour diffusion of
Unit cell dimensions
a = 11.1663(5) Å
b = 11.1663(5) Å
c = 48.724(5) Å
diethyl ether into a methanol solution of complex 1.
2
Synthesis of [CuL (µ1,3-N
)]
3 ∞
(2): Caution! Azide com-
pounds are potentially explosive and should be handled with
care and in small quantities. In particular, copper(II) azide is
explosive and in those reactions where an excess of copper(II)
salt is used, followed by addition of azide ions, an excess of
azide should be avoided.
3
3
Volume
Z, Calculated density
Absorption coefficient
F(000)
6075.3(7) Å
8, 1.473 Mg/m
1.444 mm
2800
1.67 to 25.00°
3
3
-1
-1
4.430 mm
756
1.82 to 25.00°
θ range for data
collection
Limiting indices
2
To a solution of ligand HL (0.116 g, 0.50 mmol) in methanol
(
3 mL) were added triethylamine (0.051 g, 0.50 mmol) in
-8 ≤ h ≤ 8, -25 ≤
k ≤ 26, -6 ≤ l ≤10 k ≤ 12, -57 ≤ l ≤ 57
-12 ≤ h ≤ 13, -13 ≤
methanol (3 mL) and sodium azide (0.032 g, 0.50 mmol) in
methanol (3 mL). To this resulting solution was added dropwise
a light blue solution of copper(II) tetrafluoroborate tetrahydrate
Reflections
collected/unique
Refinement method
7680/2446
42944/5349
[R(int) = 0.0725]
Full-matrix least-
squares on F
[R = 0.0444]
int
Full-matrix least-
squares on F
2
2
(0.156 g, 0.51 mmol) in methanol (3 mL), leading to the forma-
tion of a precipitate. The resulting mixture was stirred over-
night after which the violet solid was filtered off, washed with
methanol and dried in vacuo (0.110 g, yield: 66 %). Single
crystals suitable for X-ray determination were obtained by slow
evaporation of a methanol solution of complex 2.
Data/restraints/parameters
Goodness-of-fit on F
Final R indices [I > 2σ(I)]
2446/0/172
1.021
5349/0/380
1.147
= 0.0510, wR
0.1129
R = 0.0690, wR =
2
R
= 0.0319, wR
0.0631
R = 0.0531, wR
R
=
1
2
1
2
=
R indices (all data)
1
2
1
2
=
0.0694
0.1200
X-Ray crystallography: All X-ray data were collected
on a Bruker SmartApex II CCD diffractometer using graphite-
Largest diff. peak and
hole
0.375 and -0.396
0.893 and - 0.482 e
-3
-3
e Å
Å
monochromated MoK radiation (λ = 0.071073 nm). The data
α
were reduced using the SAINT program and semi-empirical
absorption corrections (SADABS) were applied. The crystal
2
structures were solved by direct methods and refined on F
by full-matrix least-squares methods with the SHELXTL-97
21
program . All non-hydrogen atoms were made anisotropic.
Hydrogen atoms were placed at calculated positions and rode
on the atoms to which they are attached (including their
isotropic thermal parameters which were equal to 1.2 times the
equivalent isotropic displacement parameter for the attached
non-hydrogen atom). Crystallographic data have been deposited
with the Cambridge Crystallographic Data Centre (reference
numbers CCDC 927118 and 927119). A summary of the key
crystallographic information is given in Table-1.
RESULTS AND DISCUSSION
The copper(II) complexes of the deprotonated tridentate
1
–
2
–
1
2
ligands (L ) and (L ) , [CuL (µ-Br)]
(
∞
(1) and [CuL (µ1,3-N
3
)]
∞
2
1
2), were synthesized in methanol by mixing HL /HL ,
Fig. 1. Perspective view of the polymeric chain structure of the complex
triethylamine, the appropriate copper(II) salt and sodium azide
for 2, as the desired co-ligand). The X-ray crystal structure
determinations reveal that complexes 1 and 2 are mono(µ-
bromo)-bridged (for 1) or mono(µ1,3-azido)-bridged (for 2)
copper(II) 1D chain complexes (Figs. 1 and 2).
1
[
CuL (µ-Br)] (1). Thermal ellipsoids are drawn at the 30 %
∞
(
probability level. Hydrogen atoms have been omitted for clarity.
Symmetry operations A is x, 0.5-y, z-0.5; B is x, 0.5-y, z + 0.5
X-Ray crystal structures of complexes 1 and 2: Comp-
lexes 1 and 2 are isostructural. The crystal structures of 1 and
2 are shown in Figs. 1 and 2, respectively and the selected
bond lengths and angles are listed in Tables 2 and 3. Both
In the infrared spectra of complexes 1 and 2, the imine
-1
bands occur at 1637 and 1638 cm , respectively. For 2 there
-1
is also a strong and sharp band at 2044 cm which is due to
the asymmetric stretching vibration of the azide group. These
values are similar to those reported for closely related struc-
1
2
structures consist of neutral [CuL Br] (1) or [CuL N
3
] (2) units.
These units are singly bridged by the bromide ions (1) or azide
20
1
turally characterized copper(II) 1D chain complexes .
ions (2), forming polymeric 1D chain structures [CuL (µ-Br)]
∞

Vol. 25, No. 14 (2013)
Synthesis and Crystal Structures of One-Dimensional Chain Copper(II) Complexes 7869
1
–
one oxygen atom of the deprotonated tridentate ligand (L )
2
–
or (L ) and two bromide ions (1) or two nitrogen atoms from
two bridging azide ions (2), giving an N OBr (1) or N O (2)
2
2
4
coordination environment overall. The basal coordination sites
are occupied by the three donor atoms of the Schiff-base ligand
and the bromine atom Br(1) for 1 or one nitrogen atom [N(3)
or N(8)] of the azide ligand for 2, while the apical position is
occupied by the bromine atom [Br(1A)] for 1 or one nitrogen
atom [N(10) or N(5A)] of the azide ligand of the next repeating
unit. The apical Cu-Br(1A) (1) or Cu-N(azide) [Cu(1)-N(10),
Cu(2)-N(5A)] (2) bond is significantly longer than the corres-
ponding basal Cu-Br(1) (1) or Cu-N [Cu(1)-N(3), Cu(2)-N(8)]
(2) bond (Tables 2 and 3), a feature which appears frequently
Fig. 2. Perspective view of the polymeric chain structure of the complex
2
[
CuL (µ1,3-N
3
∞
)] (2). Thermal ellipsoids are drawn at the 30 %
2
3-26
in square-pyramidal copper(II) complexes . The copper
atom is located 0.1682(15) Å for 1 or 0.1063(29) and
probability level. Hydrogen atoms have been omitted for clarity.
Symmetry operations A is x, y-1, z
0
.0828(29) for 2 out of the basal plane towards the apical
TABLE-2
ligand. In the coordination polyhedron, the average value of
the Br(apical)-Cu(1)-atom(basal) angles in 1 is 94.4º, while
the corresponding value of the N(apical)-Cu(1)-atom(basal)
or N(apical)-Cu(2)-atom(basal) angles in 2 is 93º or 92.4º. In
addition the average value of the cis basal angles in 1 is 90º,
while the corresponding value of the cis basal angles in 2 is
89.9º or 90.0º. So these average angle values in 1 are very
close to those observed in 2. The bond lengths and angles in 1
and 2 compare well with the values reported for related
copper(II) complexes
Mono(µ-bromo)-bridged copper(II) chain complexes are
scarce. Only a few structurally characterized complexes have
SELECTED BOND LENGTHS (Å) AND
ANGLES (º) FOR COMPLEX 1
Cu(1)-O(1)
Cu(1)-N(2)
Cu(1)-Br(1B)
O(1)-Cu(1)-N(1)
N(1)-Cu(1)-N(2)
N(1)-Cu(1)-Br(1)
1.901(2)
2.115(3)
Cu(1)-N(1)
Cu(1)-Br(1)
1.950(3)
2.4225(8)
4.4313 (8)
176.59(11)
90.34(7)
2.9977(9)
92.18(11)
84.42(12)
162.10(10)
Cu(1)···Cu(1A)
O(1)-Cu(1)-N(2)
O(1)-Cu(1)-Br(1)
N(2)-Cu(1)-Br(1)
92.98(8)
90.87(8)
Br(1)-Cu(1)-Br(1A) 106.52(4) Br(1A)-Cu(1)-O(1)
Br(1A)-Cu(1)-N(1)
Cu(1)-Br(1)-Cu(1B) 109.22(4)
Symmetry transformations used to generate equivalent atoms: A is x,
.5-y, z-0.5 and B is x, 0.5-y, 0.5 + z.
91.17(10) Br(1A)-Cu(1)-N(2) 88.94(10)
19,20,24,27-30
.
–
–
0
24,27,28,31
been reported to date
is the most unusual feature of the crystal structure for complex
. The basal and apical Cu-Br bond lengths in complex 1 are
close to those observed in these reported chain examples
2.382-2.469 Å for basal Cu-Br bond and 2.856-3.027 Å for
. The polymeric 1D chain structure
TABLE-3
SELECTED BOND LENGTHS (Å)
AND ANGLES (º) FOR COMPLEX 2
1
Cu(1)-O(1)
Cu(1)-N(2)
Cu(1)-N(10)
Cu(2)-N(6)
1.904(5)
1.921(5)
2.788(6)
2.044(5)
1.975(6)
5.5823 (13)
93.9(2)
168.1(3)
83.9(2)
92.5(2)
80.2(2)
124.2(5)
93.4(2)
168.9(2)
85.8(2)
Cu(1)-N(1)
Cu(1)-N(3)
Cu(2)-O(2)
Cu(2)-N(7)
Cu(2)-N(5A)
Cu(2)···Cu(1A)
O(1)-Cu(1)-N(3)
O(1)-Cu(1)-N(1)
N(1)-Cu(1)-N(3)
N(1)-Cu(1)-N(10)
N(3)-Cu(1)-N(10)
N(9)-N(10)-Cu(1)
O(2)-Cu(2)-N(8)
O(2)-Cu(2)-N(6)
N(6)-Cu(2)-N(8)
2.108(6)
1.973(6)
1.894(4)
1.939(5)
2.830(6)
5.6694 (13)
90.8(2)
177.4(2)
91.1(2)
88.5(2)
110.6(2)
114.6(4)
90.3(2)
178.8(2)
90.7(2)
(
apical Cu-Br bond). In 1 the Cu-Br-Cu angle is 109.22(4)º,
which lies in the reported range 102.2-134.0º. Correspondingly,
the intrachain minimum Cu···Cu separation, 4.431 Å, is in the
literature range 4.189-4.851 Å.
In the 1D chain structure of complex 2 the basal Cu-
N(azide) bond lengths [1.973(6) Å for Cu(1)-N(3), 1.975(6)
Å for Cu(2)-N(8)] are close to those observed in the reported
Cu(2)-N(8)
Cu(1)···Cu(2)
O(1)-Cu(1)-N(2)
N(2)-Cu(1)-N(3)
N(1)-Cu(1)-N(2)
O(1)-Cu(1)-N(10)
N(2)-Cu(1)-N(10)
N(4)-N(3)-Cu(1)
O(2)-Cu(2)-N(7)
N(7)-Cu(2)-N(8)
N(6)-Cu(2)-N(7)
O(2)-Cu(2)-N(5A)
N(5A)-Cu2-N(7)
N(9)-N(8)-Cu(2)
N(8)-N(9)-N(10)
20,29,32-34
chain examples
. However, the apical Cu-N(azide) bond
lengths [2.788(6) Å for Cu(1)-N(10) and 2.830(6) Å for Cu(2)-
N(5A)] are significantly longer than literature values (2.355-
2.621 Å) for the related chain structures. This indicates that
2
[CuL N
3
] units are weakly linked through the end-to-end azide
91.53(19) N(5A)-Cu(2)-N(6)
87.5(2)
bridges, resulting in a 1D chain polymer. The intrachain mini-
mum Cu···Cu separations, 5.5823(13) Å for Cu(1)-Cu(2) and
5
78.7(2)
123.1(4)
177.9(7)
N(5A)-Cu(2)-N(8)
N4-N5-Cu(2A)
N(3)-N(4)-N(5)
111.7(2)
115.3(5)
176.8(7)
.6694(13) Å for Cu(1)-Cu(2A), are similar to the literature
values reported for related singly azide-bridged copper(II)
chain structures.
Symmetry transformations used to generate equivalent atoms: A is x,
y-1, z.
Thermal stability: Thermogravimetric analyses were
carried out on complexes 1 and 2 from room temperature to
1000 ºC in air with a heating rate of 10 ºC min . The TGA
2
(
1) and [CuL (µ1,3-N
3
)] (2). For 2 two crystallographically
∞
2
-1
independent consecutive [CuL N
3
] units are present in the chain
structure. The azide ions bridge these repeating double units
in an end-to-end fashion.
curves are shown in Fig. 3. The TGA curve for complex 1
shows that 1 decomposed in four steps. The first step in the
temperature range of 29-320 ºC accompanied with weight loss
of 21.12 % (calcd. 21.21 %). This may be attributed to the
loss of a bromide ion. The second step took place within the
temperature range 320-450 ºC with weight loss of 10.87 %
In both cases the arrangement of donor atoms around
copper(II) centre can be described as a distorted square pyramid
according to the Addison τ values of 0.24 for 1 and 0.16 for
22
2
. Each copper ion is coordinated to two nitrogen atoms and

7
870 Zhang et al.
Asian J. Chem.
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Trans., 6014 (2008).
2
found weight loss of 22.23 % (calcd. 23.61 %).
Conclusion
25. R. Li, P. Zhao, G. Tang and X. Tang, Acta Crystallogr., C64, m339 (2008).
6. R. Li, B. Moubaraki, K.S. Murray and S. Brooker, Eur. J. Inorg. Chem.,
851 (2009).
2
Two copper(II) complexes of phenol-containing tridentate
Schiff base ligands (L ) and (L ) in the forms of [CuL (µ-Br)]
2
1
–
2
–
1
∞
27. S.J. Brown, X. Tao, T.A. Wark, D.W. Stephan and P.K. Mascharak,
2
(
1) and [CuL (µ1,3-N
3
)]
∞
(2) have been synthesized and charac-
Inorg. Chem., 27, 1581 (1988).
2
2
8. R. Cortés, L. Lezama, J.I.R. de Larramendi, G. Madariaga, J.L. Mesa,
F.J. Zuñiga and T. Rojo, Inorg. Chem., 34, 778 (1995).
9. S. Naiya, C. Biswas, M.G.B. Drew, C.J. Gómez-García, J.M. Clemente-
Juan and A. Ghosh, Inorg. Chem., 49, 6616 (2010).
terized. Single crystal X-ray structure determinations carried
out on 1 and 2 reveal that both complexes are mono(µ-bromo)-
bridged (for 1) or mono(µ1,3-azido)-bridged (for 2) square
pyramidal copper(II) one-dimensional chain polymeric comp-
lexes. Thermogravimetric analysis results show that complex
30. M. He, W. Zhang and Z. Yu, Inorg. Chim. Acta, 363, 3619 (2010).
3
3
3
1. A. Pajunen and S. Pajunen, Acta Chem. Scand., A40, 413 (1986).
2. Z.-L. You, X.-L. Ma and S.-Y. Niu, J. Coord. Chem., 61, 3297 (2008).
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Chem., 33, 1013 (2008).
2
is more stable than complex 1.
ACKNOWLEDGEMENTS
The authors acknowledged the financial support for this
3
4. C.-Y. Wang, J.-Y.Ye, C.-Y. Lv, W.-Z. Lan and J.-B. Zhou, J. Coord. Chem.,
6
2, 2164 (2009).
work by the Scientific Research Foundation for the Returned
Overseas Chinese Scholars, State Education Ministry, Huai'an
Industry-University-Institute Cooperation Foundation
(HAC201014) and Jiangsu Key Laboratory for the Chemistry
of Low-Dimensional Materials (JSKC12108).