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ARTICLE

DOI: 10.1002/zaac.201200327

Transition Metal Complexes with the Schiff Base Ligand


1-{[2-(2-Hydroxyethylamino)ethylimino]methyl}naphthalen-2-ol
Mei-Ju Niu,*[a] Huan-Huan Li,[a] Su-Na Wang,[a] Zhi-Qiang Cao,[a] Da-Wei Sun,[a] and
Jian-Min Dou[a]
Keywords: N-(2-hydroxyethyl)-ethylenediamine; 2-Hydroxy-1-naphthaldehyde; Schiff bases; Supramolecular structure
Abstract. Six transition metal compounds [Cu(H2L)(CH3COO)]H2O
(1), [Cu(H2L)(CH3COO)] (2), [Cu(H2L)](ClO4)CH3OH (3),
2[Cu(H2L)2] (4), [Co(H2L)2](NO3)2CH3OH (5), and [Ni(H2L)](NO3)
(6) were synthesized by reactions of the Schiff base ligand H3L
(1-{[2-(2-hydroxyethyl
amino)ethylimino]methyl}naphthalen-2-ol)
with the corresponding metal salts and characterized by single crystal

X-ray diffraction, elemental analysis, IR and UV/Vis spectroscopy and


TG analysis. All compounds are mononuclear molecules, in which the
Schiff base ligand exhibits diverse coordination modes and conformations. The NHO, OHO, and CHO inter- and intramolecular
hydrogen bonding interactions link these molecules into multidimensional network supramolecular structures.

Introduction

[Co(H2L)2](NO3)2CH3OH (5), and [Ni(H2L)](NO3) (6)


(Scheme 1) were obtained. The Schiff base ligand behaves as
a versatile chelating agent exhibiting variable denticity toward
metal ions depending upon the requirements of the metal ions.
It behaves as either a tridentate NNO donor set or a tetradentate NNOO chelating mode. Fascinatingly, multidimensional
network supramolecular structures also were observed in all
structures formed by hydrogen-bonding interactions, which
may contribute to the additional stability of the metal compounds.

Organometallic compounds of Schiff bases have played a


vital role in coordination chemistry, mainly due to their ease
of preparation, structural variability and widespread applications such as catalysts, functional materials, antibacterial
reagents[16] etc. The salen-type tetradentate ligand H3hase
{1-[(2-hydroxy-ethyl)amino]-2-(2-(salicydeneamino)ethane}
is especially attractive because of the imine C=N group and
the hydroxyl OH group. The OH group can act as both hydrogen-bonding acceptor and donor and may thus facilitate the
formation of multi-dimensional supramolecular networks. Several transition metal compounds based on H3hase, such as vanadium(III), chromium(III), manganese(III), iron(III), and cobalt(III) were reported.[711] To the best of our knowledge, only
a few crystal structures of metal compounds with naph-type
Schiff base ligands have been reported.[1217]
In our continuing investigation on this interesting system, we
herein report the systematic preparation and characterization of a
family of mononuclear compounds with the ligand H3L [H3L =
(1-{[2-(2-hydroxyethylamino)ethylimino]methyl}naphthalen2-ol)] (Scheme 1) and explore how the Schiff base ligands are
modified by coordination to different metal ions and which
factors have an influence on the structure. Six complexes,
namely: [Cu(H2L)(CH3COO)]H2O (1), [Cu(H2L)(CH3COO)]
(2), [Cu(H2L)](ClO4)CH3OH (3), 2[Cu(H2L)2] (4),
* Prof. Dr. M.-J. Niu
Fax: +86-0635-8239121
E-Mail: niumeiju@163.com
[a] Shandong Provincial Key Laboratory of Chemical Energy Storage
and Novel Cell Technology
School of Chemistry and Chemical Engineering
Liaocheng University
Liaocheng 252059, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201200327 or from the author.

414

Results and Discussion


Syntheses
The mononuclear complexes were prepared by simple reactions that involve deprotonation of the ligand in ethanol or
methanol:dichloromethane (v:v = 2:1) followed by complexation with the corresponding metal salt at room temperature
and slightly basic pH. To get more examples for the investigation of the important factors determining the structure, we
chose different types of metal salts as bridging or counter
anions to control the resulting compounds. Compounds 1 and
2 were synthesized using copper(II) acetate monohydrate as
the starting material, and the acetate group acts as monodentate
ligand. In compound 3, copper(II) perchlorate hexahydrate was
substituted for CuII(CH3COO)2H2O, the perchlorate iron balanced the charge of the compound species and participated in
the construction of the overall supramolecular networks, the
same accounted for the nitrate anions in compounds 5 and 6.
During the reaction, the CoII ion in compound 5 may be oxidized by oxygen to CoIII.
Most of the compounds are colored and stable in air, soluble
in DMSO, DMF, MeOH, and EtOH but poorly soluble in diethyl ether.

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Z. Anorg. Allg. Chem. 2013, 639, (2), 414423

Transition Metal Complexes with a Schiff Base Ligand

Scheme 1. Schematic depiction of the syntheses of the compounds.

Description of the Structures


Crystal Structure of [Cu(H2L) (CH3COO)]H2O (1) and
[Cu(H2L)(CH3COO)] (2)
Single crystal X-ray diffraction indicates that compound 1
crystallizes in the orthorhombic space group Pbca. As shown
in Figure 1, the asymmetric unit is composed of one CuII ion,
one deprotonated Schiff base ligand, one acetate anion as well
as one water molecule. The CuII ion is four-coordinate through
three donor atoms (Namine, Nimine, Ophen) of the deprotonated
Schiff base ligand and one oxygen atom of the monodentate
acetate anion. The sum of the angles around the copper atom
is 357.2 (Table 1), which indicates a slightly distorted squareplanar arrangement. The distortion may also be conveniently
measured by the trans angles [O2Cu1N1 = 172.0(2) and
N2Cu1O3 = 169.4(2)], which are ideally 180 for a squareplanar compound and 109.5 for a tetrahedral compound.[18]
Deviations of the least-square mean planes passing through
O2, N1, N2, O3 donor atoms is 0.145, 0.137, 0.148,
0.135 , respectively. It is noteworthy that the oxygen atom
O1 of the phenol group uncoordinated to CuII ions in H2L has
strong intramolecular hydrogen bonding with uncoordinated
O4 atom of the carboxyl group [O4O1 = 2.641(7) ].
Compound 2 crystallizes in the monoclinic space group P21.
As shown in Figure 2, compound 2 is neutral and has the molecular formula [Cu(H2L)(OAc)], where H3L acts as a tridentate ligand bound through Namine, Nimine, Ophen atoms. The
fourth and fifth coordination sites are occupied by the monodentate acetate anion and the hydroxyl oxygen atom. The trans
angle [173.85(13)], the angles in the basal plane [84.94(15)
94.74(13)] and the apical to basal angles [72.47(12)
106.29(12)], all indicate a slightly distorted square pyramidal
Z. Anorg. Allg. Chem. 2013, 414423

Figure 1. Molecular structure of compound 1.

arrangement around Cu1. The Cu1O1 distance of 2.644(2)


is longer, and attributable to a weak binding as well as an
increase in the coordination number from four to five.
Along with subtle differences in ligand conformation as well
as presence of an additional water molecule in the lattice affects their supramolecular structure in both two structures.
For compound 1, strong hydrogen-bonding interaction N1
H1CO4 gives rise to a 1D chain along the b axis (Figure 3).
Interestingly, the packing of adjacent chains results in the formation of one-dimensional channels viewed down the crystallographic b axis, in which solvent water molecules are alternatingly filled (Figure 4). Within compound 2, weak non-conventional hydrogen bonding CHO including C4H4BO2
(x, y+1, z), C9H9O2 (x, y1/2, z+1), C5H5O1 (x+1,
y+1/2, z+1) and C3H3AO1 (x, y+1, z) are responsible for
the formation of 2D layer arrangements (Figure 5). The details
of hydrogen bonding parameters are presented in Table 2.

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Table 1. Selected bond lengths / and angles / for compounds 16.
1
Cu(1)O(2)
Cu(1)N(2)
O(2)Cu(1)N(2)
O(2)Cu(1)O(3)
N(2)Cu(1)O(3)

1.913(5)
1.927(5)
91.5(2)
89.0(2)
169.4(2)

Cu(1)O(3)
Cu(1)N(1)
O(2)Cu(1)N(1)
N(2)Cu(1)N(1)
O(3)Cu(1)N(1)

1.952(4)
2.022(6)
172.0(2)
84.7(2)
96.0(2)

1.905(3)
1.924(4)
2.644(3)
91.70(14)
162.92(13)
84.94(15)
103.67(12)
89.79(12)

Cu(1)O(3)
Cu(1)N(1)

1.955(3)
2.034(4)

O(2)Cu(1)O(3)
O(2)Cu(1)N(1)
O(3)Cu(1)N(1)
N(2)Cu(1)O(1)
N(1)Cu(1)O(1)

89.99(13)
173.85(13)
94.74(13)
106.29(12)
72.47(12)

1.871(3)
1.900(3)
94.53(12)
94.84(11)
169.43(13)

Cu(1)O(1)
Cu(1)N(1)
O(2)Cu(1)N(1)
N(2)Cu(1)N(1)
O(1)Cu(1)N(1)

1.980(3)
1.987(3)
179.25(12)
86.20(13)
84.41(12)

1.874(3)
1.887(3)
2.001(3)
1.877(3)
1.888(3)
2.003(3)
88.49(13)
88.95(13)
176.90(14)
177.26(14)
93.14(13)
85.78(14)
178.76(14)

Cu(2)O(8)
Cu(2)N(8)
Cu(2)N(5)
Cu(2)N(6)
Cu(2)O(6)
Cu(2)N(7)
O(8)Cu(2)N(6)
N(6)Cu(2)N(5)
O(6)Cu(2)N(5)
O(8)Cu(2)N(7)
N(6)Cu(2)O(6)
N(8)Cu(2)N(5)
N(6)Cu(2)N(8)

1.870(3)
1.896(3)
1.993(4)
1.886(3)
1.896(3)
2.011(4)
87.72(15)
85.40(14)
176.55(15)
177.56(14)
92.88(14)
93.97(15)
178.95(17)

1.872(5)
1.881(5)
1.894(6)
90.3(2)
88.6(2)
179.9(3)

Co(1)N(3)
Co(1)N(4)
Co(1)N(2)
O(3)Co(1)N(3)
N(1)Co(1)N(2)

1.898(6)
1.995(6)
2.008(6)
92.7(2)
85.5(2)

1.821(6)
1.835(7)
95.8(3)
87.1(3)
170.9(3)

Ni(1)O(2)
Ni(1)N(2)
O(1)Ni(1)N(2)
O(1)Ni(1)O(2)
N(2)Ni(1)O(2)

1.953(7)
1.918(7)
176.9(3)
91.7(3)
85.6(3)

2
Cu(1)O(2)
Cu(1)N(2)
Cu(1)O(1)
O(2)Cu(1)N(2)
N(2)Cu(1)O(3)
N(2)Cu(1)N(1)
O(2)Cu(1)O(1)
O(3)Cu(1)O(1)
3
Cu(1)O(2)
Cu(1)N(2)
O(2)Cu(1)N(2)
O(2)Cu(1)O(1)
N(2)Cu(1)O(1)
4
Cu(1)O(4)
Cu(1)N(4)
Cu(1)N(1)
Cu(1)O(2)
Cu(1)N(2)
Cu(1)N(3)
O(4)Cu(1)O(2)
O(4)Cu(1)N(1)
O(4)Cu(1)N(3)
O(2)Cu(1)N(1)
O(2)Cu(1)N(2)
N(2)Cu(1)N(1)
N(4)Cu(1)N(2)
5
Co(1)O(3)
Co(1)O(1)
Co(1)N(1)
O(3)Co(1)O(1)
O(1)Co(1)N(4)
N(1)Co(1)N(3)
6
Ni(1)O(1)
Ni(1)N(1)
O(1)Ni(1)N(1)
N(1)Ni(1)N(2)
N(1)Ni(1)O(2)

Crystal Structure of [Cu(H2L)](ClO4)CH3OH (3)


The structure of 3 is shown in Figure 6. Selected bond
lengths and angles are outlined in Table 1. Compound 3 crystallizes in the monoclinic space group P21/c. The asymmetry
unit contains a [Cu(H2L)]+ cation, a ClO4 anion as well as
one free CH3OH molecule. The coordination environment
around the CuII atom is formed by four donors of the partially
deprotonated Schiff base ligand. The CuN2O2 chromophore is
nearly planar and the trans bond angles are 179.25(12) for
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O2Cu1N1; 169.43(13) for N2Cu1O1. The ligand acts in


a tetradentate fashion, constructing a six-membered chelate
ring with phenolate binding and another five-membered ring
with alkoxo binding. The OCuN angles of 94.5(1) (in the
chelating ring) and 94.8(1) (inter-ring) are close to 90. Considering that some constraint can be imposed by the bite of the
chelating ligand.
It is noteworthy that a non-coordinated perchlorate anion
acts as counterion and participates in the hydrogen bonding,
thus stabilizing the overall structure. The perchlorate ion acts

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Transition Metal Complexes with a Schiff Base Ligand

as hydrogen bonding acceptor from C1 and C5 atoms of the


adjacent units (C1H1BO4, C1H1AO3, and C5H5O5),
resulting into a 1D belt structure. Adjacent belts are further
joined together through weak OHO hydrogen bonding involving C3H3BO6 to form a 2D architecture (Figure 7).
The details of hydrogen bonding parameters are presented in
Table 2.

Crystal Structure of 2[Cu(HL)2] (4)

Figure 2. Molecular structure of compound 2.

Figure 3. 1D long-chain structure along b axis of compound 1. Hydrogen bonds are marked by dashed lines.

Figure 4. Packing diagram of 1 showing one-dimensional channels


viewed down the crystallographic b axis. The channels are alternatingly filled by solvent H2O molecules.

Compound 4 crystallizes in the triclinic space group P1.


There are two crystallographically independent Cu(H2L)2 molecules A (Figure 8) and B (see Supporting Information, Figure
S1), each molecule consists of one CuII atom and two partially
deprotonated Schiff base ligands. The two molecules in the
asymmetric unit are almost identical. Selected bond lengths
and angles are outlined in Table 1. The Cu1II ion is hexacoordinate with a [N4O2] octahedral environment furnished by two
imine nitrogen atoms (N2 and N4), two amine nitrogen atoms
(N1 and N3), and two deprotonated phenol oxygen atoms (O2
and O4) from two Schiff base ligands. Among them, the atoms
O2, N1, N2, and N4 define the equatorial plane, from which
Cu(1) deviates by 0.0144(17) . The axial sites are occupied
by phenol O4 and amine N3 [O4Cu1N3 = 176.90(14)]; The
CuO and CuN bond lengths in the equatorial plane
[1.877(3)2.001(3) ] are slightly shorter than the corresponding ones in the axial position [1.874(3)2.003(3) ], which
clearly indicate the nature of distortion in the coordination
sphere. The distortion associated with the Jahn-Teller effect of
CuII with a d9 electron configuration.[19,20]
It is noteworthy that two Schiff base ligands have two free
CH2OH groups, which are involved in the weak CHO interactions. The uncoordinated hydroxyl oxygen atom O(1), O(5)
act as a acceptor to C50, C39 atom with C50H50O1 and
C39H39O5, which link the independent molecules to exhibit a 2D sheet structure parallel to the bc plane. The resulting
3D supramolecular network (Figure 9) is further extended by
the weak CH interactions C12H12Cg1 (with HCg
distance of 3.15 and an angle of 140.5; Cg1 is the centroid
of a ring constituted by C5156; symmetry code: x, y, z). Hydrogen bonding parameters are presented in Table 2.

Crystal Structure of [Co(H2L)2](NO3)2CH3OH (5)

Figure 5. Intermolecular association of compound 2 by CHO interactions into a supramolecular network. Hydrogen bonds are marked
by dashed lines.
Z. Anorg. Allg. Chem. 2013, 414423

Single-crystal X-ray analysis reveals that compound 5 crystallizes in the monoclinic crystal system, space group C2/c.
The asymmetric unit includes a [Co(H2L)2]+ cation and a NO3
anion, and two free CH3OH molecules, charge balance is afforded by NO3 anion in the lattice (Figure 10). Selected bond
lengths and angles are outlined in Table 1. Considering the
charge balance, the cobalt ion should have been oxidized aerobically from oxidation state +2 to +3. Similar oxidation has
been observed in previous compounds,[21] in which all the central metal atoms are trivalent and adopt octahedral coordination
arrangement. The central CoIII atom is hexacoordinate in a dis-

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M.-J. Niu et al.

ARTICLE
Table 2. Hydrogen bonding arrangements /, for compounds 16.
DHA

d(HA)

d(DA)

(DHA)

Symmetry code

N(1)H(1C)O(4)
O(1)H(1)O(4)

2.20(7)
1.85

2.960(8)
2.641(7)

153(6)
162.0

x, y1, z

N(1)H(1)O(4)
C(4)H(4B)O(2)
C(9)H(9)O(2)
C(5)H(5)O(1)
C(3)H(3A)O(1)

2.15
2.58
2.64
2.68
2.60

2.938(5)
3.525(5)
3.347(5)
3.453(5)
3.525(6)

144.6
163.9
133.5
139.1
158.9

x, y+1, z
x, y+1, z
x, y1/2, z+1
x+1, y+1/2, z+1
x, y+1, z

C(1)H(1B)O(4)
C(5)H(5)O(5)
C(3)H(3B)O(6)
C(1)H(1A)O(3)

2.61
2.72
2.69
2.67

3.397(6)
3.583(5)
3.394(6)
3.392(6)

138.0
155.3
130.2
131.5

x+2, y+1/2, z+3/2


x+2, y1/2, z+3/2
x, y+3/2, z1/2

C(12)H(12)Cg1

3.15

3.914(12)

140.5

C(39)H(39)O(5)
C(50)H(50)O(1)

2.52
2.59

3.237(12)
3.504(9)

134.0
168.2

x, y, z
Cg1: the centroid of ring C51C56
x1, y, z
x+1, y+2, z+1

C(26)H(26)O(6)
C(5)H(5)O(5)
C(28)H(28B)O(7)

2.67
2.72
2.68

3.295(14)
3.540(12)
3.433(14)

125.5
148.2
134.3

x1/2, y +1/2 ,z
x+1/2, y+1/2, z+3/2
x+1, y+1, z+2

C(14)H(14B)O(3)
C(6)H(6)O(4)
C(13)H(13A)O(5)
C(15)H(15A)O(3)
C(10)H(10)Cg2

2.49
2.71
2.77
2.68
2.59

3.450(14)
3.323(13)
3.210(14)
3.174(15)
3.489(8)

172.2
124.6
108.4
112.0
164.1

x, y1/2, z+1/2
x+1, y1/2, z+3/2
x, y+3/2, z+1/2
x, y, z+1
x+1, y + 1/2, z+5/2
Cg2: the centroid of ring C3C8

Figure 6. Molecular structure of compound 3, the crystal methanol


molecule was omitted for clarity.
Figure 8. Molecular structure of fragment A.

Figure 7. 2D architecture of compound 3. Hydrogen bonds are marked


by dashed lines.

torted octahedral N4O2 environment. As illustrated in Figure 10, the ligands are partially deprotonated and act meridional tridentate chelate mode forming fused 65 chelating rings.
The two ligands are arranged in such a way that the imine-N
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atoms are in trans positions, while the phenoxo oxygen atoms


and the amino nitrogen atoms are cis.[7] The elongation of
trans CoN bonds relative to CoO can be ascribed to the
trans influence of the CoO bonds.[18] Neither of alcohol
groups are coordinated, but positioned cis to each other, forming hydrogen bonds with the nitrate anion.
Uncoordinated NO3 anion, which act as connectors, plays
a vital role in the construction of supramolecular structures by
weak CHO hydrogen bonding. The nitrate oxygen atoms
O(5), O(6), and O(7) act as a triple hydrogen bonding acceptor
from the carbon atoms C5, C26, and C28 from different molecules C5H5O5 (symmetry code: x+1/2, y+1/2, z+3/2)
[2.72 , 3.540(12) , 148.2], C26H26O6 (symmetry code:
x1/2, y+1/2, z) [2.67 , 3.295(14) , 125.5] and C28

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Transition Metal Complexes with a Schiff Base Ligand

Figure 11. 2D supramolecular sheet structure of compound 5. Hydrogen bonds are marked by dashed lines.
Figure 9. 3D structure of compound 4. Hydrogen bonds are marked
by dashed lines.

Figure 12. Molecular structure of compound 6 along with the atom


numbering scheme. The counter anion nitrate is also shown.

Figure 10. Molecular structure of compound 5, two crystal methanol


molecules were omitted for clarity.

H28BO7 (symmetry code: x+1, y+1, z+2) [2.68 ,


3.433(14) , 134.3]. Selected hydrogen bonding parameters
are presented in Table 2. As a result, 2D supramolecular sheet
structure is formed which is displayed in Figure 11.

In the crystalline state, no classic hydrogen bonding was


detected. The mononuclear units in 6 are assembled alongside
each other through the weak CH C10H10Cg2 ring interaction [2.585(3) , 164.1; where Cg2 is the centroid of ring
constituted by C3C8 atoms; symmetry code: x+1, y+1/2,
z+5/2] leading to a 1D chain along the b axis. The resulting
2D supramolecular sheet structure (Figure 13) is held together
through NO3 via weak C6H6O4, C13H13AO5, C14
H14BO3, and C15H15AO3 interactions. Nitrate anions
act as pillars to connect and stabilize the overall structure. The
details of hydrogen bonding parameters are presented in
Table 2.

Crystal Structure of [Ni(H2L)] (NO3) (6)


The structure of compound 6 is depicted in Figure 12. The
asymmetric unit consists of one [Ni(H2L)]+ cation and one free
nitrate anion. The coordination environment around the central
NiII atom is nearly square-planar. The Schiff base ligand acts
as a negatively charged tetradentate N2O2 chelate by binding
through one phenol oxygen atom [Ni1O1 = 1.821(6) ], one
imine nitrogen atom [Ni1N1 = 1.835 (7) ], one amine nitrogen atom [Ni1N2 = 1.918(7) ], and one deprotonated alkoxo
oxygen atom [Ni1O2 = 1.953(7) ]. The sum of the angles
around NiII is exactly 360.2, suggesting that the Ni1, N1, N2,
O1, and O2 atoms are nearly coplanar. Selected bond lengths
and angles are outlined in Table 1
Z. Anorg. Allg. Chem. 2013, 414423

Discussion of the Structures


The structural characterization of the products reveals that
the Schiff base ligand tends to act as a tridentate (tetradentate)
ligand, which coordinates to d-block transition metals through
the phenol oxygen, imine nitrogen, and amine nitrogen (alkoxo
oxygen) atoms to afford stable mononuclear compounds
(square-plane, square pyramid, octahedron arrangement). The
main advantage in the use of Schiff base ligands relates to
the semi-rigid element of the CH2 and NH groups, which
produce different types of molecules. Depending on the coordination requirement of the central metal atoms (shape, coordination number, radius), the ligand can adopt different confor-

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ARTICLE

Figure 13. 2D sheet network structure of compound 6 through weak


CH and CHO interactions. Hydrogen bonds are marked by
dashed lines.

mations by bending, stretching, or twisting patterns, respectively, which is confirmed by the configuration of the ligands
in the compounds (see Supporting Information, Figure S2). In
compounds 4 and 5, two Schiff base ligands are arranged in cis
position, the alcohol group cannot participate in coordination
because of the bridging feature and steric effects of ligands.
Yet, the unsaturated coordination sites of the metal ions in mononuclear compounds 1 and 2 are occupied by a secondary
acetate ligand. In addition, although oxygen-rich anions such
as nitrate or perchlorate are not coordinated to metal atoms in
the other compounds, they are involved in hydrogen bonding.
It can effectively tune the structural diversities through different anions. The final supramolecular assemblies formed
through NHO, OHO hydrogen bonds and weak CHO,
CH interactions. It is influenced by coordinating mode of
the ligand used; metal-ligand ratio; nature of the counterions;
and various experimental conditions such as the solvents, temperature, and crystallization methods.
IR and Absorption Spectra
A strong sharp band observed at 1632 cm1 is attributed to
the (C=N) group of the ligand.[22] Also, the characteristic
peak at = 8.79 ppm in the 1H NMR spectrum further confirms the CH=N condensation. However, a downshift of the
(C=N) band in all the compounds (16181630 cm1) indicated coordination via the azomethine nitrogen (MN).[21]
The broad band at ca.3400 cm1 is due to OH stretching vibrations of the free hydroxyl group in both ligands and compounds. The absorptions at 32653275 cm1 in the spectrum
of the ligand demonstrate the formation of OHN intramolecular hydrogen bonds. The strong absorption bands of ArO
in the Schiff base at 1280 cm1,[23] are located at lower frequencies for the compounds, viz. 1180 cm1 for 1 and 2,
1197 cm1 for 3, 1130 cm1 for 4, 1176 cm1 for 5, and
1234 cm1 for 6, respectively, indicates that the phenol OH
oxygen is coordinated to the metal ion with deprotonation.
Compounds 1 and 2 have two intense absorption bands at 1574
420

www.zaac.wiley-vch.de

and 1363 cm1, 1579 and 1361 cm1, respectively, corresponding to the asymmetric and the symmetric stretching bands in
carboxylates, with value being 211 and 218 cm1, reflecting
the monodentate nature of the coordinated acetate group.[24] In
compound 3, two bands at 1094 cm1 (the asymmetric ClO
stretching mode, 3) and 622 cm1 (the asymmetric ClO
bending mode, 4) indicates the presence of uncoordinated
perchlorate anion.[25] In the spectrum of compounds 5 and 6,
we also note a very strong band at 1384 cm1 (1) attributed
to free nitrate ion (NO) stretching vibration absorption, provides good evidence that nitrate ions were not involved in coordination.[26]
The compounds display three main absorption bands (see
Supporting Information, Figure S3). The absorption bands observed within the high-energy region 246255 nm are most
probably due to the intra-ligand * transitions of the
naphthalene rings and the azomethine moiety.[27] The absorption bands in the range of 311317 nm correspond to n*
transition upon coordination of the ligand. The intense and
broad bands in the 383396 nm region are attributable to a
ligand-to-mental charge transfer (LMCT) transition,[28] which
further supports coordination of the ligands to the transition
metal ion via the oxygen atoms.

Thermal Properties (TG/DTG)


The thermal stability of the compounds was investigated
with TGA. The thermal behaviors of six compounds were almost the same. Hence, the representative TG/DTG of copper(II) compounds 1 and 3 are discussed herein. The TGA
curve of compound 1 showed the first gradual weight loss of
this compound occurs at about 50 C, corresponding to the loss
of free water molecule[29] (found. 4.529 %, calcd. 4.507 %); the
second weight loss in the region 164350 C corresponds to
the loss of Schiff base moiety with mass loss of 64.6 % (calcd.
64.9 %). The complete decomposition of the compound occurs
at 355 C. Compound 3 underwent similar decomposition process. The first weight loss of 4.2 % from 68.4 C to 162 C
corresponds to the loss of the free methanol molecule (calcd.
6.1 %) and the decomposition of the compound begins at
261 C.

Conclusions
The syntheses, structures and characterization of a series of
novel mononuclear transition metal compounds are reported
herein. The Schiff-base ligand displays flexible chelating
modes, e.g. within compounds 1, 4, and 5, it is tridentate
(NNO donor set), where the alcohol groups are not bonded,
and within compounds 2, 3, and 6, it exhibits a tetradentate
fashion utilizing the N2O2 donor set. Versatile hydrogen bonds
interactions lead to the formation of 1D, 2D, 3D supramolecular networks, which contribute to the additional stability of
structures. The thermal stabilities of compounds 1 and 3 were
discussed.

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Z. Anorg. Allg. Chem. 2013, 414423

Transition Metal Complexes with a Schiff Base Ligand

Experimental Section
General: All chemicals were of reagent grade quality obtained from
commercial sources and used without further purification. The melting
points were obtained with an X-4 digital micro melting-point apparatus
and were uncorrected. IR spectra were measured as KBr pellets with
a Nicolet-5700 spectrophotometer in the 4000400 cm1 region. Elemental analyses (C, H, N) were performed with a PE-2400II apparatus.
1
H and 13C NMR spectra were obtained with a Varian Mercury Plus
400 MHz NMR spectrometer. Thermal analyses were performed with
a TGA SDTA 851e thermogravimetric analyzer, with a heating rate of
10 Kmin1 in a nitrogen atmosphere. UV/Vis spectroscopic measurement of the methanol solution of the compound was carried out with
a Shimadzu UV-2550 spectrophotometer.
Caution! Copper perchlorate is potentially explosive and should be
handled in small quantities and very carefully.
Synthesis of the Schiff Base Ligand (H3L): The methanol solution
of 2-hydroxy-1-naphthaldehyde (1.7218 g, 10 mmol) was added to a
methanol solution (10 mL) of N-(2-hydroxyethyl)ethylenediamine
(1.0934 g, 10.5 mmol). The mixed solution was heated to reflux under
vigorous stirring for 4 h and left to stand overnight at refrigerator. The
resulting yellow precipitate was filtered and rinsed with cold ethyl
alcohol and ethyl ether, and finally dried in vacuo to give the ligands
H3L. Yield: 87 %. M.p.: 144146 C. C15H18N2O2 (Mr = 258.32): C
69.52 (calcd. 69.74); H 6.81 (7.02); N 10.97 (10.84) %. IR (KBr): =
3438, 3270, 2923, 1632, 1384, 1362, 1312, 1280, 1141, 1126, 1080,
994, 619, 545, 514 cm1. 1H NMR (400 MHZ, CDCl3, 25 C): =
8.79(s, 1 H, CH=N), 7.227.88(m, 6 H, C10H6), 5.29(s, 1 H, OH),
3.643.74(m, 4 H, CH2), 2.833.02(m, 4 H, CH2OH), 1.57(m, 1
H, NH) ppm.
[Cu(H2L)(CH3COO)]H2O (1): An amount of copper (II) acetate
monohydrate (0.1996 g, 1 mmol) was added dropwise to a methanol
and dichloromethane solution (v:v = 2:1) containing the Schiff base
ligand H3L (0.2580 g, 1 mmol) under vigorous stirring. The reaction
mixture was stirred for 4 h and filtered. The resulted dark green solution was allowed to stand at the room temperature. After three days
dark green crystals were obtained at the bottom of the vessel. The
crystals were isolated and washed with diethyl ether three times. Yield:
71 %. (on the basis of H3L used). M.p.:160162 C. C17H22CuN2O5
(Mr = 397.91): C 50.79 (calcd. 51.31); H 5.13(5.57); N 7.57(7.04) %.
IR (KBr): = 3437, 3273, 2924, 1630, 1574, 1540, 1415, 1384, 1363,
1180, 1120, 1091, 597, 559, 503, 474, 437 cm1. UV/Vis (CH3OH),
max/nm: 248, 317, 390.
[Cu(H2L)(CH3COO)] (2): In the same way, the resulting deep blue
solution was filtered and the impurities were removed, afterwards anhydrous diethyl ether (5 mL) was layered onto the filtrate in the tube.
Blue block-shaped single crystals of 2 suitable for X-ray analysis were
obtained after one week. Yield: 68 % (on the basis of H3L used). M.p.:
257262 C. C17H20CuN2O4 (Mr = 379.89): C 53.42 (calcd. 53.75); H
5.11 (5.31); N 7.63 (7.37) %. IR (KBr): = 3438, 3270,2926, 1624,
1579, 1528, 1417, 1385, 1361, 1180, 1146, 1067, 834, 589, 546, 462
cm1. UV/Vis (CH3OH), max/nm: 246, 315, 383.
[Cu(H2L)(ClO4)]CH3OH (3): Green crystals of compound 3 were
obtained in similar manner to compound 1 by replacing copper(II)
acetate monohydrate with copper(II) perchlorate hexahydrate. Yield:
71 % (on the basis of H3L used). M.p.: 180184 C. C16H21ClCuN2O7
(Mr = 452.34): C 41.51 (calcd. 42.48); H 4.47 (4.68); N 6.77 (6.19) %.
Z. Anorg. Allg. Chem. 2013, 414423

IR (KBr): = 3428, 3270, 2948, 1628, 1435, 1415, 1386, 1197, 1147,
1094, 984, 650, 622, 582, 498, 477, 458, 423 cm1. UV/Vis (CH3OH),
max/nm: 249, 317, 384.
2[Cu(H2L)2] (4): Similarly, copper(II) chloride dihydrate (0.85 g,
0.5 mmol) and H3L (0.2583 g, 1 mmol) yield the product as bluish
green crystals in methanol and dichloromethane after one week. Yield:
68 % (on the basis of copper(II) chloride dihydrate used). M.p.:180
184 C. C60H68Cu2N8O8 (Mr = 1156.30) C62.54 (calcd. 62.32); H 5.78
(5.92); N 9.58 (9.69) %. IR (KBr): = 3447, 3265, 2944, 1630, 1541,
1407, 1386, 1181, 1083, 975, 823, 736, 649, 603, 568, 511, 477, 418
cm1. UV/Vis (CH3OH), max/nm: 247, 314, 395.
[Co(H2L)2](NO3)2CH3OH (5): Similarly, cobalt (II) nitrate hexahydrate (0.1450 g, 0.5 mmol) and H3L (0.2583 g, 1 mmol) yield the product as dark brown crystals in methanol and dichloromethane after 3 d.
Yield: 62 %. (on the basis of cobalt(II) nitrate hexahydrate used). M.p.:
172174 C. C31H38CoN5O8 (Mr = 667.59); C 54.51 (calcd. 55.77); H
5.45 (5.74); N 11.27 (10.49) %. IR (KBr): = 3439, 3269, 2922, 1627,
1418, 1384, 1176, 1059, 997, 858, 619, 503, 446 cm1. UV/Vis
(CH3OH), max/nm: 251, 314, 396.
[Ni(H2L)](NO3) (6): In the same way, an ethanol solution (10 ml) of
nickel nitrate hexahydrate (0.29 g, 1 mmol) was added dropwise to
an ethanol solution (10 ml) containing Schiff base ligand (0.2583 g,
1 mmol) under vigorous stirring. Orange-red block-shaped single crystals suitable for X-ray analysis were obtained after two weeks. Yield:
67 % (on the basis of H3L used). M.p.:258262 C. C15H17N3NiO5 (Mr
= 378.03); C 47.82 (calcd. 47.66); H 4.64 (4.53); N 11.28 (11.11) %.
IR (KBr): = 3424, 3268, 2946, 1618, 1511, 1384, 1234, 1129, 984,
859, 778, 752, 698, 545, 427 cm1. UV/Vis (CH3OH), max/nm: 255,
311, 389.
X-ray Crystal Structure Determinations: All data were collected
with a Bruker SMART CCD1000 diffractometer with graphite monochromated Mo-K radiation ( = 0.71073 ) at 298(2) K. A semiempirical absorption correction was applied to the data. The structures
were determined by direct methods and the refinement of anisotropic
thermal parameters based on full-matrix least-squares techniques on
F2 were performed using the programs SHELXS-97 and SHELXL97,[30] respectively. All non-hydrogen atomic positions were located in
difference Fourier maps and were refined anisotropically. Hydrogen
atoms were placed in calculated positions and allowed to ride on their
parent atoms. For 4, O3 and O3 which were found to be disordered
and refined isotropically to the occupancy of 0.684/0.316; for 5, O4
and O4 were disordered and refined isotropically to the occupancy of
0.57/0.43. The quality of the structure determination of 6 is poor,
which may be due to the poor quality of the crystal chosen for data
collection, and the poor data set obtained. Unfortunately, we could not
grow single crystals of 6 that were any better than the one used for
the present study, as they were the best we could acquire.[31] For depictions of the molecular structures, the program DIAMOND was employed.[32] Pertinent crystallographic data and structure refinement parameters are given in Table 3.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-763660, -867342, -763661, -763665, -763669, and
-867343. (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk,
http://www.ccdc.cam.ac.uk)

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.zaac.wiley-vch.de

421

M.-J. Niu et al.

ARTICLE
Table 3. Crystal data collection and structure refinement parameters for compounds 16.

Formula
Crystal system
Space group
M
a /
b /
c /
/
/
/
V /3
Z
T /K
/
Dcalc /mgm3
Crystal size /mm
Theta range /
Reflections collected / unique
Rint
R1,wR2
[I 2(I)]
Ra)(all data)

C17H22CuN2O5
orthorhombic
Pbca
397.91
21.6353(19)
6.3701(8)
25.447(2)
90
90
90
3507.1(6)
8
298(2)
0.71073
1.507
0.42 0.38 0.30
1.8625.01
16862 / 3091

C17H20CuN2O4
monoclinic
P2(1)
379.89
10.502(6)
6.587(4)
12.935(8)
90
107.123(8)
90
855.1(9)
2
298(2)
0.71073
1.475
0.43 0.16 0.08
2.9725.01
4392 / 2840

C16H21ClCuN2O7
monoclinic
P21/c
452.34
9.508(3)
11.987(3)
16.434(5)
90
100.700(3)
90
1840.3(9)
4
298(2)
0.71073
1.633
0.47 0.46 0.40
2.1225.02
9044 / 3250

C60H68Cu2N8O8
triclinic
P1
1156.30
12.1351(12)
16.5616(14)
16.7800(15)
71.9180(10)
69.0020(10)
85.349(2)
2991.2(5)
2
298(2)
0.71073
1.284
0.39 0.18 0.13
1.2925.02
15661 / 10373

C31H38CoN5O8
monoclinic
C2/c
667.59
21.827(2)
20.597(2)
16.7029(19)
90
119.731(2)
90
6520.7(12)
8
298(2)
0.71073
1.360
0.42 0.36 0.17
1.6125.02
16727 / 5721

C15H15N3NiO5
monoclinic
P21/c
378.03
15.3758(13)
8.5191(5)
12.1025(11)
90
103.3450
90
1542.5(2)
4
298(2)
0.71073
1.619
0.38 0.31 0.30
2.7225.02
7452 / 2701

0.0961
0.0538, 0.1416

0.0333
0.0379, 0.0745

0.0461
0.0406, 0.1003

0.0242
0.0650, 0.1745

0.1029
0.0780, 0.1961

0.1566
0.1016, 0.2392

0.1144, 0.2135

0.0483, 0.0782

0.0716,0.1219

0.1043, 0.1966

0.1787, 0.2787

0.1454, 0.2819

a) R1 = (|FoFc|)/|Fo|. wR2 = {[w(|FoFc|) ]/[w|Fo| ]} .


2

1/2

Supporting Information (see footnote on the first page of this article):


Molecular structure of fragment B of compound 4. Overlay of the
ligands in the six compounds. Electronic spectra of the compounds at
room temperature.

Acknowledgements
We acknowledge the financial support of the Natural Science Foundation of Shandong Province (Nos. ZR2010BQ021 and 2011YD02093),
the Natural Science Foundation of China (No. 20971063).

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2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Received: July 17, 2012


Published Online: November 30, 2012

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