Synthesis, characterization and spectroscopy studying of some metal complexes of a new Schiff base ligand; X-ray crystal structure, NMR and IR investigation of a new dodecahedron Cd(II) complex

Article abstract of DOI:10.1016/j.molstruc.2016.05.096

Some new [Cd(H₂L¹)(NO₃)]ClO₄ (1), [Mn(H₂L¹)](ClO₄)₂ (2), [Ni(H₂L¹)](ClO₄)₂ (3) and [Cu(H₂L¹)](ClO

Full text of DOI:10.1016/j.molstruc.2016.05.096

Accepted Manuscript
Synthesis, characterization and spectroscopy studying of some metal complexes of
a new Schiff base ligand; X-ray crystal structure, NMR and IR investigation of a new
dodecahedron Cd(II) complex
Reza Golbedaghi, Majid Rezaeivala, Maryam Khalili, Behrouz Notash, Javad Karimi
PII:
S0022-2860(16)30566-X
10.1016/j.molstruc.2016.05.096
MOLSTR 22610
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 6 May 2016
Revised Date: 26 May 2016
Accepted Date: 27 May 2016
Please cite this article as: R. Golbedaghi, M. Rezaeivala, M. Khalili, B. Notash, J. Karimi, Synthesis,
characterization and spectroscopy studying of some metal complexes of a new Schiff base ligand; X-ray
crystal structure, NMR and IR investigation of a new dodecahedron Cd(II) complex, Journal of Molecular
Structure (2016), doi: 10.1016/j.molstruc.2016.05.096.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
1
2
Synthesis, characterization and spectroscopy studying of some metal
complexes of a new Schiff base ligand; X-ray crystal structure, NMR
and IR investigation of a new dodecahedron Cd(II) complex
3
4
5
6
7
8
9
Reza Golbedaghi*,a, Majid Rezaeivalab, Maryam Khalilia, Behrouz Notashc , Javad Karimid
aChemistry Department, Payame Noor University, 19395-4697 Tehran, Iran
bDepartment of Chemical Engineering, Hamedan University of Technology, Hamedan 65155, Iran
cDepartment of Chemistry, Shahid Beheshti University, G.C., Evin, Tehran, 1983963113, Iran
dDepartment of Chemistry, Ferdowsi University of Mashhad, Iran
10
11
12
13
14 Abstract
15
16
17
18
19
20
21
22
23
24
25
26
Some new [Cd(H2L1)(NO3)]ClO4 (1), [Mn(H2L1)](ClO4)2 (2), [Ni(H2L1)](ClO4)2 (3) and
[Cu(H2L1)](ClO4)2 (4) complexes were prepared by the reaction of a Schiff base ligand and M
(II) metal ions in equimolar ratios (M = Cd, Mn, Ni and Cu). The ligand H2L1 was synthesized
by reaction of 2-[2-(3-formyl phenoxy)propoxy]benzaldehyde and ethanol amine and
1
characterized by IR, H,13C NMR spectroscopy and elemental analysis. The synthesized
13
complexes were characterized with IR and elemental analysis in all cases and 1H, CNMR, and
X-ray in the case of Cd(II) complex. The X-ray crystal structure of compound 1 showed that all
nitrogen and oxygen atoms of Schiff base ligand (N2O4) and a molecule of nitrate with two donor
oxygen atom have been coordinated to the metal ion and the Cd(II) ion is in an eight-coordinate
environment that is best described as a distorted dodecahedron geometry
27
28
Keywords: Schiff base ligand, Complex, Ethanol amine, Crystal structure, X-ray, Dodecahedron
29
30
Corresponding author, Tel.: +98 (813)2542400; fax: +98 (852)4246001; Email:
golbedaghi82@gmail.com (R. Golbedaghi)
31
1

ACCEPTED MANUSCRIPT
32 1.
Introduction
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
We are interested in the polydentate coordination chemistry of different metal ions and we have
a number of publications of macrocyclic [1, 2] and macroacyclic [3-7] Schiff base complexes.
Recently Schiff base compounds have been extensively employed as ligands for mono- or
multinuclear macrocyclic or macroacyclic metal complexes, which are applicable to biomimetic
catalysts, transporter agents, magnetic or electronic functional materials, building materials in
nano-space construction and so on [8-10]. In addition, during the last few decades there has been
great interest in synthesis of new Schiff base ligands and their coordination chemistry. This
interest comes from the fact that Schiff base ligands and their complexes show remarkable
biological activities including antibacterial, tumor, fungal, microbial, oxidant, cancer, diabetic,
analgesic, and anti-HIV properties [11-17]. Herein, we continue the study of the various
complexes which show characteristic architecture and properties depending on the conformation
of the Schiff base ligand. In addition, we are interested in the polydentate coordination chemistry
of different metal ions specially Cd(II), Mn(II), Ni(II) and Cu(II) complexes and we have studied
their complexes containing multidentate ligands [1-7]. In the current work, we report the
synthesis and characterization of Cd(II), Mn(II), Ni(II) and Cu(II) complexes with a new
macroacyclic Schiff base ligand derived from the 2-[2-(3-formyl phenoxy)propoxy]
benzaldehyde. After synthesis the Schiff base ligand and preparation some new complexes, we
tried to get appropriate crystals of them. Finally, the suitable crystals of Cd(II) complex were
prepared and we successes to take its X-ray analysis data. The X-ray crystal structure shows
distorted dodecahedron geometry for Cd(II) metal ion.
2

ACCEPTED MANUSCRIPT
55 2. Experimental
56
57
2.1. General Information
58
59
60
61
62
Hydrated metal salts and ethanol amine were obtained from Aldrich and were used without
further purification. 2-[2-(3-formyl phenoxy)propoxy]benzaldehyde (H2L1) was prepared via
literature method [18]. IR and NMR spectra were measured on a Perkin Elmer FT-IRGX and a
Bruker DPX 300 spectrometer, respectively.
63
2. 2. X-ray crystal structure determination
64
65
66
67
68
69
70
71
72
73
74
Single crystal X-ray data on complex 1 were collected at 120 K on a Bruker SMART APEX
CCD diffractometer using graphite monochromated Mo Kα radiation (λ = 0.71073 Å). The linear
absorption coefficients, scattering factors for the atoms, and the anomalous dispersion
corrections were taken from the International Tables for X-ray Crystallography [19]. The data
integration and reduction were carried out with SAINT [20] software. Empirical absorption
correction was applied to the collected reflections with SADABS [21] and the space group was
determined using XPREP [22]. The structure was solved by the direct methods using SHELXTL-
97 [23] and refined on F2 by full-matrix least-squares using the SHELXL-97 program [24]
package. All non-hydrogen atoms were refined anisotropically. The hydrogen atoms attached to
carbon atoms were positioned geometrically and treated as riding atoms using SHELXL default
parameters.
75
76
2.3. Synthesis
3

ACCEPTED MANUSCRIPT
77
78
2.3.1. Preparation of Aldehydes
1, 3-dibromo propane (0.1 mol) and NaOH (0.2 mol) were mixed and heated under reflux in 500
ml equas ethanol (300 ml H2O and 200 ml EtOH). Salsylaldehyde (0.2 mol) in 30 ml EtOH was
added and heated under reflux for 4 days. After cooling the resulting yellow crystals were
filtered, washed and recrystallized [18].
79
80
81
82
83
84
2.3.1. Preparation of ligand H2L1
Aldehyde (0.284 g, 1mmol) and ethanol amine (0.122 g, 2 mmol) were mixed and heated in the
85
86
87
88
89
90
91
92
93
94
40 ºC for 30 min in EtOH (30ml). The solution was filtered and the filtrate was reduced to ca 10
cm3. Yellow crystalline compound was obtained washed with cooled ethanol and dried. Yield:
54%. Anal. Calc. for C21H26N2O4: C, 67.85; H, 6.84; N, 7.91. Found: C, 67.44; H, 6.79; N,
1
17.81. IR (KBr, cm-1): 1638 (νC=N Schiff base), 1490 (νC=C), 3365 (νOH). HNMR (DMSO,
ppm, 300 MHz): δ 2.36 (m, 2H), 3.71 (t, 4H), 3.82 (t, 4H), 4.25 (t, 4H), 6.99 (m, 2H), 7.40 (m,
2H) 7.96 (m, 2H), 7.99 (m, 2 H), 875 (s, 2H), 13CNMR (DMSO, ppm, 300 MHz): δ 62.48 (C-1),
63.57 (C-2), 65.03 (C-3), 76.73(C-4), 77.05(C-5), 112.20, 121,09, 125.62, 125,74, 12684,
127.40, 132.16 (Aromatic Rings), 158.88 (Schiff base).
2.3.3. Preparation of complex [CdH2L1(NO3)]ClO4 (1)
95
96
97
98
99
This complex was prepared by reaction of ligand H2L1 and Cd(NO3)2.4H2O. Ligand H2L1 (0.370
g, 1mmol) was solved in 10 ml methanol and the solution was stirred at 30-40 ºC. Cd(NO3)2.
4H2O (0.308 g, 1mmol) dissolved in MeOH (5 ml) was subsequently added. The mixture was
stirred at 50–60 ºC for24 h, then NaClO4 (0.28 g, 2 mmol) was added. The solution was filtered
and the filtrate was reduced to ca. 10 cm3. A crystalline compound was obtained by slow
4

ACCEPTED MANUSCRIPT
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
diffusion of Et2O vapor into this solution. Yield of the complex [CdH2L1(NO3)]ClO4 (1), 75%.
Anal. Calc. for (C21H25CdClN3O11): C, 39.10; H, 4.10; N, 6.50. Found: C, 38.78; H, 3.89; N,
3.76%. IR (KBr, cm-1): 1682 (νC=N Schiff base), 1456 (νC=C), 3445 (νOH), 1384 (νN-O), 1111
(νClO4). 1HNMR (DMSO, ppm, 300 MHz): δ 2.09 (m, 2H, 1-H), 2.55 (t, 4H, 2-H), 2.67(t, 4H, 3-
H), 3.05 (t, 4H, 4-H), 6.97(2H), 7.14(4H), 7.41(2H), 8.63 (s, 2H, Schiff base). 13CNMR (DMSO,
ppm, 300 MHz): δ60.65 (C-1), 63.71 (C-2), 64.78 (C-3), 68.75(C-4). 112.69, 120.54, 126.66 and
131.94, (Aromatic Rings), 156.67 (Schiff base).
2.3.4. Preparation of complex [Mn(H2L1)](ClO4)2 (2)
Compound 2 was prepared in an analogous method to 1. Yield of the complex
[Mn(H2L1)](ClO4)2 (2), 66%. Anal. Calc. for (C21H26MnCl2N2O12): C, 40.38; H, 4.16; N, 4.48.
Found: C, 39.86; H, 4.03; N, 4.18%. IR (KBr, cm-1): 1643 (νC=N Schiff base), 1604 (νC=C),
1106 (νClO4), 3431 (νOH).
2.3.6. Preparation of complex [Ni(H2L1)](ClO4) (3)
Compound 3 was prepared in an analogous method to 1. Yield of the complex
[Ni(H2L1)(NO3)]ClO4 (3), 67%. Anal. Calc. for (C21H26NiCl2N2O12): C, 40.12; H, 4.14; N, 4.45.
Found: C, 39.79; H, 4.06; N, 4.29%. IR (KBr, cm-1): 1652 (νC=N Schiff base), 1598 (νC=C),
1108 (νClO4), 3420 (νOH).
2.3.6. Preparation of complex [Cu(H2L1)](ClO4)2 (4)
Compound 4 was prepared in an analogous method to 1. Yield of the complex
[Cu(H2L1)(NO3)]ClO4 (4), 67%. Anal. Calc. for (C21H26CuCl2N2O12): C, 39.84; H, 4.10; N, 4.42.
5

ACCEPTED MANUSCRIPT
123
124
125
Found: C, 39.28; H, 4.02; N, 4.31%. IR (KBr, cm-1): 1639 (νC=N Schiff base), 1599 (νC=C),
1068 (νClO4), 3535 (νOH).
126 3. Result and discussion
127
3.1. Synthesis and characterization
128
129
130
131
132
133
All complexes 1-4 were synthesized by the reaction of Schiff base H2L1 Cd(II), Mn(II), Ni(II)
and Cu(II) metal ions, respectively (Schemes 1). The Schiff base ligand was characterized by IR,
1
elemental analysis and H,13CNMR and the resulting complexes were characterized by IR and
elemental analysis in all cases and 1H,13CNMR and X-ray crystal structure in the case of Cd(II).
The complexes are quite stable in air and can be stored in a desiccator for long periods of time
without decomposition.
134
135
3.2. IR Study
136
137
138
139
140
141
142
143
144
Condensation of all the primary amino group is confirmed by the lack of N–H stretching bands
in the IR reign (3150–3450 cm-1) and the presence of strong C=N (Schiff base) stretching bands
at 1638 cm-1 for Schiff base ligands H2L1. Also the stretching bands of C=N (imine) complexes
1-4 have been observed at 1649, 1643, 1652 and 1639 cm-1 respectively (Fig. 1). As it can be
seen the bands related to the imine groups in Schiff bases have been shifted in the IR for all
complexes and it can show that the donor atoms in ligands have been coordinated to the metal
ions and the complexes have been formed. The bands observed at 1363 and 1674 cm-1 in the IR
of complex 1 can be assigned to the asymmetric bidentate nitrate group. A broad intense band at
-
-1
ca. 1105 cm-1 due to ClO4 shows no splitting, indicating the absence of coordination of ClO4
6

ACCEPTED MANUSCRIPT
145
146
for all complexes. The NMR studies of Schiff base ligands and synthesized complexes are
completely consistent with their formulation.
147
148
3.3. X-ray crystal structure analysis
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
As mentioned previously, the Cd(II) complex of ligand H2L1 was prepared and the fine and
suitable crystals of 1 were obtained by slow diffusion of diethyl ether vapor into a methanol-
ethanol solution of the corresponding complex. A summary of the details of the crystal data, data
collection and refinement details is given in Table 1. ORTEP diagram of the molecular structure
of 1 is shown in Fig. 2. with the atomic numbering. Selected bond lengths and bond angles are
listed in Table 2. The Cd–O (O aldehyde and hydroxy) and Cd–N bond lengths (N imine) are
within the normal range. The crystal structure of 1 consists of a cadmium metal center
coordinated to two nitrogen and four oxygen donor atoms from Schiff base ligand and two
oxygens from the nitrate ion. Eight-coordinate systems are found to adopt a cube, a square
antiprism or a triangulated dodecahedron (TD) arrangement [25]. On the basis of the observed
angles, (N–Cd–N, N–Cd–O and O–Cd–O), complex 1 adopts a slightly distorted TD geometry
[25]. The two Cd–O distances [2.430 and 2.402 Å] in the cadmium complex differ substantially,
one being long and the other short. The Cd–O distance for the bidentate nitrate group (av. 2.531
Å) is comparable with the calculated mean value [2.416(144) Å] observed in 28 eight-coordinate
Cd(II) complexes obtained from the Cambridge Structural Database [26], navigated using
CONQUEST [27], thus both oxygen atoms are coordinated to the central cadmium ion. The Cd–
N distances are in the normal range [from 2.246(3) to 2.262(3) Å]. Both Cd–Nimine bond lengths
are shorter (2.246(3) and 2.262(3) Å) than Cd–O bond lengths. The bond distance between the
7

ACCEPTED MANUSCRIPT
167
168
169
170
171
172
173
174
175
176
177
atom Cd(1) and the O(1), 2.499(3) Å and O(2), 2.647 (2) Å is longer than the bond distance
between Cd(1) and O(3), 2.430(2) Å and O(4) 2.457 (2) Å. Also, The longest and shortest bond
angles are related to O(6)–Cd–O(1), 153.82º and O(7)–Cd–N(1), 50.93 º respectively. In
addition, the longest angles between the Nimine and oxygen atoms are related to theN(2)–Cd(1)–
O(2) and N(1)– Cd(1)–O(6), 139.44 º and 126.75 º respectively. The X-ray crystal structure
showed that there are five rings that three of them are six membered and both of them are five
membered. The five membered rings almost are cis together, there are no manly different
between the bond angles in all rings. The bond angles in six membered rings are, 77.00º, 72.45º
68.23º for N(2)–Cd(1)–O(3), O(2)–Cd(1)–O(3) and O(2)–Cd(1)–N(1) respectively. As same as,
the bond angles in five member rings are 71.82º and 73.53º for O(1)–Cd(1)–N(1) and O(4)–
Cd(1)–N(2) respectively.
178
179
3.4. NMR spectra
180
181
182
183
184
185
186
The NMR spectra of the cadmium complex confirm the formation of a fully condensed Schiff
base ligand and cadmium complex. The appeared peaks in 1H and 13CNMR of Schiff base ligand
show that the ligand has been synthesized and is pure and the comparison of shifted peaks in
Cd(II) complex spectrum (1H and 13CNMR) with appeared peaks in the HMR spectrum of ligand
show the donor atoms (N2O4) have been coordinated to the Cd(II) metal ion. The 13CNMR of the
ligand and complex shows five distinct methylene carbons in the aliphatic region. It is interesting
that the 1HNMR spectrum of this complex shows two kinds of protons for the methylene group.
187
188
4. Conclusion
8

ACCEPTED MANUSCRIPT
189
190
191
192
193
194
195
196
197
198
199
200
201
202
The synthesis and characterization of a new Schiff base ligand and a number of M(II) complexes
(M= Cd, Mn, Ni, Cu) are reported. The NMR of ligand and Cd(II) complex were studied; also
the molecular structure of complex 1 has been determined by single crystal X-ray diffraction and
has been shown dodecahedron coordinated Cd(II) ion.
Acknowledgment
We are grateful to the Payame Noor and Shahid Beheshti Universities for financial support.
Appendix A. Supplementary data
CCDC 1463846 contains the supplementary crystallographic data for complex 1. These data can
be obtained free of charge via http://www.ccdc.cam.ac.uk/ contains/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44)1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
203
204
References
[1] R. Golbedaghi, S. Salehzadeh, H. Keypour, A.G. Blackman, Polyhedron 29 (2010) 850-856.
205
206
[2] R. Golbedaghi, S. Salehzadeh, H. R. Khavasi, A.G. Blackman, Polyhedron 68 (2014) 151-
156.
207
208
209
210
211
212
213
[3] S. Salehzadeh, R. Golbedaghi, A.G. Blackman, Journal of Coordination Chemistry 63 (2010)
634-642.
[4] S. Salehzadeh, R. Golbedaghi
2532-2539.
,
H.R. Khavasi, Journal of Coordination Chemistry 62 (2009).
9

ACCEPTED MANUSCRIPT
214
215
216
[5] R. Golbedaghi, M. Rezaeivala, L. Albeheshti, Journal of Molecular Structure 1076 (2014)
673-678.
217
218
[6] R. Golbedaghi, E. Alavipour, Journal of Molecular Structure 1099 (2015) 286-290.
219
220
[7] R. Golbedaghi, S. Moradi, S. Salehzadeh, A.G. Blackman, Journal of Molecular Structure
1108 (2016) 727-734.
221
[8] P. Guerriero, S. Tamburini, and P.A. Vigato, Coord. Chem. Rev. 139 (1995) 17-243.
222
223
[9] T.R. Youkin, E.F. Connor, J.I. Henderson, S.K. Friedrich, R.H. Grubbs and D.A.
Bansleben, Science 287 (2000) 460-462.
224
[10] C.F. Works and P.C. Ford, J. Am. Chem. Soc. 1222 (2000) 7592-7593.
225
226
227
228
229
230
231
232
233
234
235
236
237
[11] A.M.A. Alaghaz, M.E. Zayed, S.A. Alharbi, J. Mol. Struct. 1083 (2015) 430-440.
[12] M. Sönmez, M. Çelebi, İ. Berber, Eur. J. Med. Chem. 45 (2010) 19351939.
[13] N.A. Negm, M.F. Zaki, Colloids Surf. B. 64 (2008) 179185.
[14] S. Yadav, R.V. Singh, Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 78 (2011) 298-304.
[15] G. Kumar, S. Devi, R. Johari, D. Kumar, Eur. J. Med. Chem. 52 (2010) 269-276.
[16] A.N. Kursunlu, E. Guler, F. Sevgi, B. Ozkalp, J. Mol. Struct. 1048 (2013) 476-481.
[17] Ö. Güngör, P. Gürkan, J. Mol. Struct. 1074 (2014) 62-68.
238
[18] I.M. Atkinson, K.A. Byriel, P.S.K. Chia, C.H.L. Kennard, A.J. Leong, L.F. Lindoy, M.P.
10

ACCEPTED MANUSCRIPT
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
Lowe, S. Mahendran, G. Smith, G. Eei, Aust. J. Chem. 51 (1998) 985-989.
[19] International Tables for X–Ray Crystallography; Kynoch Press: Birmingham, England, III,
1952.
[20] SAINT, version 6.02; Bruker AXS: Madison, WI, 1999.
[21] G.M. Sheldrick, SADABS: Empirical Absorption Correction Program, University of
Göttingen, Göttingen, Germany, 1997.
[22] XPREP, version 5.1; Siemens Industrial Automation Inc.: Madison, WI, 1995.
[23] G.M. Sheldrick, SHELXTL Reference Manual, version 5.1; Bruker AXS: Madison, WI,
1997.
[24] G.M. Sheldrick, SHELXL-97: Program for Crystal Structure Refinement, University of
Gottingen, Gottingen, Germany, 1997.
[25] J.R. Gispert, Quimica de coordination, Omega, Barcelona, 2000.
[26] I.J. Bruno, J.C. Cole, P.R. Edington, M. Kessler, C.F. Macrae, P. Mccabe, J. Pearson, R.
Taylor, Acta Crystallogr., Sect. B. 58 (2002) 389-391.
[27] F.H. Allen, Acta Crystallogr., Sect. B. 58 (2002) 380-382.
270
271
272
273
274
11

ACCEPTED MANUSCRIPT
275
276
Table 1. Crystal data and structure refinement for compound 1
Empirical formula
Formula weight
C21H25CdClN3O11
643.30
Temperature (K)
120
Wavelength(A)
Crystal system
Space group
0.71073
Triclinic
p-1
Unit cell dimensions
a (Å )
9.829(2)
b (Å)
11.411 (2)
c (Å)
13.489 (3)
α
95.15 (3)
β
102.24 (3)
γ
113.62 (3)
1328.6(6)
V (A3)
Z
2
Dcalc (Mg/m3)
1.608
F(000)
650
Crystal size (mm3)
θ range for data collection (°)
Index ranges
0.3x 0.25 x 0.17
2.33–29.17°
-13<=h<=12, -15<=k<=15,
0<=l<=18
Reflections collected
Independent reflections
Ri
7109
4300
0.016
Absorption correction
Max. and min. transmission
Refinement method
restraints
Numerical
0.410 and 0.223
Least-squares matrix: full on F2
0
Final R indices [I>2sigma(I)]
R indices (all data )
Largest diff. peak and hole (e.Å-3)
R1 = 0.0406, wR2 = 0.0942
R1 = 0.0501, wR2 = 0.0972
1.785 and -1.045
277
278
279
280
12

ACCEPTED MANUSCRIPT
281
282
283
284
Table 2. Selected bond lengths (Å) and bond angles (°) for compound 1
Bond lenghts (Å)
N1—Cd1
N2—Cd1
O1—Cd1
O2—Cd1
O3—Cd1
O4—Cd1
O5—Cd1
1
2.262 (3)
2.246 (3)
2.499 (3)
2.647 (2)
2.430 (2)
2.457 (2)
2.402 (2)
2.607 (3)
O6—Cd1
Bond angle (°)
N1—Cd1—N2
N1—Cd1—O5
N2—Cd1—O5
N1—Cd1—O3
N2—Cd1—O3
O5—Cd1—O3
N1—Cd1—O4
N2—Cd1—O4
O5—Cd1—O4
O3—Cd1—O4
N1—Cd1—O2
N2—Cd1—O2
O5—Cd1—O2
O3—Cd1—O2
O4—Cd1—O2
N1—Cd1—O1
N2—Cd1—O1
O5—Cd1—O1
O3—Cd1—O1
O4—Cd1—O1
O2—Cd1—O1
O6—Cd1—O1
O6—Cd1 —O2
O6—Cd1—N1
O6—Cd1—O4
N2—Cd1—O6
O5—Cd1—O6
O3—Cd1—O6
152.24 (10)
92.79(10)
92.53(11)
120.44(9)
77.00(9)
126.05(8)
80.90(9)
73.53(10)
78.43(9)
142.41(8)
68.23(8)
139.44(9)
84.62(8)
72.45(7)
143.89(8)
71.82(9)
92.72(11)
154.84(8)
79.09(8)
79.52(10)
106.74(8)
153.82(8)
70.54(8)
126.75(9)
118.66(9)
76.42(11)
50.93 (8)
75.30(8)
285
13

ACCEPTED MANUSCRIPT
286
287
1
4
O
O
O
O
EtOH
40 0C
CH
N
HC
N
2 OHCH2CH2NH2
+
COH
HOC
3
2
OH
HO
288
289
(a)
1
4
O
O
1
4
O
O
CH
N
HC
N
HC
+
Cd(NO3)2.4H2O
Cd
CH
HO
EtOH
50-60 C /24 h
N
3
OH
0
3
N
O
O
2
2
N
OH
HO
O
290
291
(b)
292
293
Scheme 1. Syntheses of the Schiff base ligand H2L1 (a) and related complex 1 and NMR
numbering (b)
294
295
296
14

ACCEPTED MANUSCRIPT
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
O
O
CH
N
CH
N
OH
HO
O
HC
N
O
CH
Mn
N
O
H
HO
O
HC
N
O
CH
Ni
N
O
H
HO
O
HC
N
O
CH
Cu
N
O
H
HO
321
322
Fig. 1. The comparison of the appeared CH=N band of ligand and synthesized complexes in IR
spectra
15

ACCEPTED MANUSCRIPT
323
324
325
(a)
326
327
328
(b)
, (a), and its view of the dodecahedron coordination
329
330
Fig. 2. X-ray crystal structure of complex
1
polyhedron (b).
16

ACCEPTED MANUSCRIPT
Highlights
1- Synthesis and characterization a new Schiff base ligand
2- Synthesis and characterization of some new complexes
3- Synthesis and X-ray analysis data of a new dodecahedron Cd(II) complex
4- NMR and IR study of a new Schiff base complex
1