Synthesis and spectral studies of macrocyclic Pb(II), Zn(II), Cd(II) and La(III) complexes by template reaction of 1,2-bis(2-formylphenyl)ethane with metal nitrate and various diamine

Article abstract of DOI:10.1134/S0036023610090111

Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis(3-aminopropoxy)butane or (±)-trans-1,2-diaminocyclohexane with metal nitrate and 1,2-bis(2-formylphenyl)ethane and their structures were proposed on the basis of elemental an

Full text of DOI:10.1134/S0036023610090111

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 9, pp. 1402–1409. © Pleiades Publishing, Ltd., 2010.
COORDINATION COMPOUNDS
Synthesis and Spectral Studies of Macrocyclic Pb(II), Zn(II),
Cd(II) and La(III) Complexes by Template Reaction
of 1,2ꢀBis(2ꢀformylphenyl)ethane with Metal
Nitrate and Various Diamine1
·
Salih Ilhana, Hamdi Temelb, Salih Pa
s
ab, and
I
brahim Te
g
ina
a Department of Chemistry, Faculty of Art and Sciences, Siirt University, Siirt, Turkey
b Department of Chemistry, Faculty of Education, Dicle University, Diyarbakir, Turkey
eꢀmail: salihsiirt@gmail.com, salihilhan@dicle.edu.tr
Received January 20, 2009
Abstract—Eight new macrocyclic complexes were synthesized by template reaction of 1,4ꢀbis(3ꢀaminoproꢀ
poxy)butane or ( )ꢀtransꢀ1,2ꢀdiaminocyclohexane with metal nitrate and 1,2ꢀbis(2ꢀformylphenyl)ethane
and their structures were proposed on the basis of elemental analysis, FTꢀIR, UVꢀVis, molar conductivity
measurements, 1H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to
be 1 : 1. The complexes are 1 : 2 electrolytes for Cd(II), Pb(II) and Zn(II) complexes and 1 : 3 electrolytes for
La(III) as shown by their molar conductivities (
ions in these complexes, such complexes are electrically conductive. The configurations of Cd(II) and Zn(II)
complexes were proposed to probably tetrahedral, La(III) complexes are octahedral and Pb(II) complexes
are octahedral geometry in the
1 complex and tetrahedral geometry in the 2 complex.
Λ
m) in DMSO at 10–3 mol –1. Due to the existence of free
L
L
L
DOI: 10.1134/S0036023610090111
1
The coordination chemistry of lanthanide(III) ions with metal nitrate and 1,2ꢀbis(2ꢀformylphenyl)ethane
in methanol. Then, spectral properties of the new
compounds were studied in detail.
is rapidly increasing, owing to the relevance of these
compounds in basic and applied researches in differꢀ
ent scientific areas ranging from chemistry to material
science, life science, etc. [1]. The coordination chemꢀ
istry of macrocyclic ligands is a fascinating area of
study for inorganic chemists [2]. Transition metal
macrocyclic complexes have received much attention
as active part of metalloenzymes as biomimic model
compounds due to their resemblance with natural proꢀ
teins like hemerythrin and enzymes [3, 4]. Schiff base
macrocycles have been of great importance in macroꢀ
cyclic chemistry [5]. There is a continued interest in
synthesizing macrocyclic complexes [6, 7] because of
their potential applications in fundamental and
applied sciences [8–10] and importance in the area of
coordination chemistry [11, 12]. The development of
the field of bioinorganic chemistry has been another
important factor in spurring the growth in interest in
macrocyclic compounds [13]. Studies on complexes of
Schiffꢀbase macrocyclic ligands with different ring
size, and number and nature of donor atoms for coorꢀ
dination with a variety of metal centers have been pubꢀ
lished [14–17]. In the present work we have syntheꢀ
sized Pb(II), Zn(II), Cd(II) and La(III) complexes by
template reaction of ( )ꢀ1,4ꢀbis(3ꢀaminoproꢀ
poxy)butane or ( )ꢀtransꢀ1,2ꢀdiaminocyclohexane
EXPERIMENTAL
Elemental analysis was carried out on a LECO
CHNS model 932 elemental analyzer. 1H NMR specꢀ
tra were recorded using a model Bruker Avance DPXꢀ
400 NMR spectrometer. IR spectra were recorded on
a Perkin Elmer Spectrum RX1 FTIR spectrometer on
KBr discs in the wave number range of 4000–400 cm–1
.
Electronic spectral studies were conducted on a Shiꢀ
madzu model 160 UV Visible spectrophotometer in the
wavelength 200–800 nm. Molar conductivity was meaꢀ
sured with a WTW LF model 330 conductivity meters,
using prepared solution of the complex in DMSO.
LC/MSꢀAPIꢀES mass spectra were recorded using an
Agilent model 1100 MSD mass spectrophotometer.
All the other chemicals and solvents were of analytical
grade and used as received.
The 1,2ꢀbis(2ꢀformylphenyl)ethane used in the
synthesis were prepared as shown in Fig. 1 [18, 19]. All
the chemicals and solvents were of analytical grade
and used as received.
To a stirred solution of 1,2ꢀbis(2ꢀformylphenyl)ꢀ
ethane (2 mmol) and metal nitrate in methanol
(50 mL) was added dropwise diamine (2 mmol) in
methanol (30 mL). The reaction was continued for 2 h
1
The article is published in the original.
1402

SYNTHESIS AND SPECTRAL STUDIES
1403
O
O
COH
OH
10 h at 150–155°C
5 h at room
temperature
Br
Br
2
+ 2KBr + H2O + CO2
+ K2CO3 +
O
O
Fig. 1. Synthesis of 1,2ꢀbis(2ꢀformylphenyl)ethane.
at 80
°
C
and 1 h at room temperature. After the reacꢀ (m, 8H, ArꢀH),
δ
= 10.40 (s, 2H, HC=N). Selected
cm–1): 3353
(H2O), 1642 (C=N),
−), 491
(La–O), 453 (La–N).
tion was completed, coloured the precipitate was filꢀ
tered and washed with methanol and, dried in air.
Yield: 39–14%.
IR data (KBr,
1384 (ionic
ΛM = 259
ν
ν
ν
ν
ν
ν
NO3
Ω
–1 mol–1 cm2. UVꢀvis (λmax, nm) (DMSO):
277, 326, 378. Mass spectrum (m/z): [801, 7.8%,
Characterization of [PbL1] [NO3]2 · H2O
[La(H2O)2L1][NO3]3]+].
Yield: 0.24 g (15.3%). Anal. Calcd. for
PbC26H34N4O10
Found: C, 40.11, H, 4.73, N, 6.93. 1H NMR (DMSOꢀ
d6, ppm): = 4.52 (H1, s, 4H), = 3.48 (H2, t, 4H,
J = 5.9), = 1.89 (H6, p, 4H, J = 6.4), = 3.52 (H5,
t, 4H, J = 7.1), = 3.59 (H4, t, 4H, J = 7.2), = 1.34
(H3, t, 4H, J = 5.8), = 3.42 (H2O), = 6.97–8.04
(m, 8H, ArꢀH), = 10.39 (s, 2H, HC=N). Selected
IR data (KBr, (H2O), 1645 (C=N),
cm–1): 3349
1384 (ionic (Pb–O), 442 (Pb–N).
−), 489
⋅
H2O: C, 39.64, H, 4.57, N, 7.11.
Characterization of [CdL1] [NO3]2 · H2O
Yield: 0.21 g (14.8%). Anal. Calcd. for
δ
δ
δ
CdC26H34N4O10
Found: C, 45.27, H, 5.25, N, 8.02. 1H NMR (DMSOꢀ
d6, ppm): = 4.36 (H1, s, 4H), = 3.44 (H2, t, 4H,
J = 5.9), = 1.94 (H6, p, 4H, J = 5.4), = 3.53 (H5,
t, 4H, J = 7.6), = 3.55 (H4, t, 4H, J = 6.2), = 1.39
(H3, t, 4H, J = 7.8), = 3.41 (H2O), = 6.97–8.02
(m, 8H, ArꢀH), = 10.38 (s, 2H, HC=N). Selected
IR data (KBr, (H2O), 1639 (C=N),
cm–1): 3362
1384 (ionic (Cd–O), 467 (Cd–N).
−), 509
⋅
H2O: C, 45.09, H, 5.20, N, 8.09.
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
ν
ν
ν
δ
δ
ν
ν
ν
NO3
ΛM = 194
mol–1 cm2. UVꢀvis (λmax, nm)
(DMSO): 277, 326, 381. Mass spectrum ): [569,
7.1%, [PbL1ꢀ(OCH2CH2OCH2)ꢀH]+]
δ
–1
Ω
ν
ν
ν
(m/z
ν
ν
ν
NO3
.
–1
ΛM = 152
Ω
mol–1 cm2. UVꢀvis (λmax, nm)
(DMSO): 276, 324, 376. Mass spectrum
m/z): [674,
Characterization of [ZnL1] [NO3]2 · 2H2O
10.3%, [Cd(L1][NO3]2]+].
Yield: 0.19 g (14.3%). Anal. Calcd. for
ZnC26H34N4O10
Found: C, 47.07, H, 5.22, N, 8.58. 1H NMR (DMSOꢀ
d6, ppm): = 4.46 (H1, s, 4H), = 3.45 (H2, t, 4H,
J = 6.2), = 1.91 (H6, p, 4H, J = 5.8), = 3.53 (H5,
t, 4H, J = 7.4), = 3.61 (H4, t, 4H, J = 6.3), = 1.34
(H3, t, 4H, J = 4.8), = 3.41 (H2O), = 6.99–8.08
(m, 8H, ArꢀH), = 10.39 (s, 2H, HC=N). Selected
IR data (KBr, (H2O), 1644 (C=N),
cm–1): 3347
1384 (ionic (Zn–O), 482 (Zn–N).
−), 522
⋅
2H2O: C, 46.92, H, 5.11, N, 8.42.
Characterization of [PbL2][NO3]2 · 2H2O
Yield: 0.31 g (15.4%). Anal. Calcd. for
δ
δ
δ
PbC22H24N4O8
Found: C, 36.86, H, 3.83, N, 7.95. 1H NMR (DMSOꢀ
d6, ppm): = 4.39 (H1, s, 4H), = 3.21 (H2, t, 2H,
J = 7.1), = 1.82 (H3, q, 4H, J = 6.6), = 1.48 (H4,
t, 4H, J = 8.4), = 3.41 (H2O), = 7.00–8.13 (m, 8H,
⋅
2H2O: C, 36.92, H, 3.92, N, 7.83.
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
ν
ν
ν
ArꢀH),
(KBr,
(ionic
ΛM = 186
δ
= 10.41 (s, 2H, HC=N). Selected IR data
ν
ν
ν
NO3
ΛM = 181
–1 mol–1 cm2. UVꢀvis (λmax, nm) (DMSO):
278, 322, 378. Mass spectrum ): [627, 1.3%,
([ZnL1][NO3]2)+
ν
cm–1): 3356
ν
(H2O), 1638
ν
(C=N), 1384
Ω
ν
−), 486
ν
(Pb–O), 439
ν
(Pb–N).
NO3
Ω
(m/z
mol–1 cm2. UVꢀvis (λmax, nm)
–1
.
(DMSO): 277, 326, 378. Mass spectrum
(m/z): [569,
1.3%, [[PbL2] H2O + 2H]+
⋅
.
Characterization of [La(H2O)2L1] [NO3]3 · H2O
Yield: 0.45 g (27.6%). Anal. Calcd. for
Characterization of [ZnL2] [NO3]2 · 2H2O
LaC26H38N5O15
Found: C, 38.31, H, 5.11, N, 8.49. 1H NMR (DMSOꢀ
d6, ppm): = 4.39 (H1, s, 4H), = 3.47 (H2, t, 4H,
J = 4.9), = 1.93 (H6, p, 4H, J = 7.4),
= 3.52 (H5, Found: C, 46.19, H, 5.08, N, 9.65. 1H NMR (DMSOꢀ
t, 4H, J = 5.3), = 3.58 (H4, t, 4H, J = 6.2), = 1.38 d6, ppm): = 4.41 (H1, s, 4H), = 3.24 (H2, t, 2H,
(H3, t, 4H, J = 6.4), = 3.42 (H2O), = 7.01–8.06
⋅
H2O: C, 38.19, H, 4.90, N, 8.57.
Yield: 0.26 g (22.6%). Anal. Calcd. for
ZnC22H24N4O8 2H2O: C, 46.07, H, 4.89, N, 9.77.
⋅
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
δ
J = 6.3), = 1.83 (H3, q, 4H, J = 5.9), = 1.47 (H4,
δ
δ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

1404
ILHAN et al.
t, 4H, J = 6.7),
δ
= 3.42 (H2O),
δ
= 6.930–8.09 (m, including water, ethanol, methanol, ethyl acetate, and
acetonitrile (Table 1).
8H, ArꢀH),
data (KBr,
(ionic
δ
= 10.38 (s, 2H, HC=N). Selected IR
cm–1): 3351
−), 526
ν
(H2O), 1646
ν
(C=N), 1384
The characteristic infrared spectrum data are given in
the experimental section. Infrared spectra of complexes
were recorded in KBr pellet from 4000 to 400 cm–1. The
broad bands within the range ca. 3370 cm–1 for all
complexes can be attributed to stretching vibrations of
ν
ν
ν
(Zn–O), 484
ν
(Zn–N).
NO3
–1
ΛM = 171
(DMSO): 278, 325, 377. Mass spectrum
5.8%, [ZnL2][NO3]2 + 3H]+]
Ω
mol–1 cm2. UVꢀvis (λmax, nm)
(m/z): [542,
.
water molecule
the complexes shows a
and the absence of a
(C=O) peak at around 1700 cm–1
ν
(H2O) [20,21]. The IR spectrum of
ν
(C=N) peak at ca. 1650 cm–1
ν
Characterization of [LaL2(H2O)2] [NO3]3 · H2O
is indicative of Schiff’s base condensation. A medium
band observed in the IR spectra of the complexes at
ca.1650 cm–1 region which is attributed to the
Yield: 0.29 g (20.0%). Anal. Calcd. for
LaC22H28N5O13
Found: C, 36.42, H, 4.01, N, 9.52. 1H NMR (DMSOꢀ
d6, ppm): = 4.34 (H1, s, 4H), = 3.21 (H2, t, 2H,
J = 6.3), = 1.79 (H3, q, 4H, J = 6.7), = 1.43 (H4,
t, 4H, J = 8.1), = 3.40 (H2O), = 6.95–8.04 (m, 8H,
= 10.37 (s, 2H, HC=N). Selected IR data
cm–1): 3348
(H2O), 1644 (C=N),
(ionic (La–O), 457 (La–N).
−), 491
⋅
H2O: C, 36.31, H, 3.85, N, 9.63.
ν
(C=N) stretch, indicating of the azomethine nitroꢀ
gen [22, 23]. The presence of several bands in the
region associated with nitrate vibrations clearly identiꢀ
fies these species as containing nitrate groups. The
absorptions of the nitrate counterions, at ca. 1460–
δ
δ
δ
δ
δ
δ
δ
1452 (ν5), 1300 (ν1)
and 1040 (ν2) cm–1, suggest the presꢀ
ArꢀH),
δ
ence of nitrate groups: a intense band at ca. 1384 cm–1
attributable to ionic nitrate, is also present [24, 25]. In
the spectra of all the complexes are dominated by
(KBr,
ν
ν
ν
1384
ΛM = 272
ν
ν
ν
NO3
Ω
–1 mol–1 cm2. UVꢀvis (λmax, nm) (DMSO):
bands between 2965–2855 cm–1 due to
(Alph.ꢀCH)
ν
278, 326, 378. Mass spectrum (m/z): [579, 1.7%,
groups. Conclusive evidence of the bonding is also
shown by the observation that new bands in the IR
spectra of the complexes appear at 525–485 cm–1 and
[LaL2ꢀ(OCH2)][NO3]ꢀ2H]+].
481–435 cm–1 assigned to
ν
(M–O) and
ν
(M–N)
Characterization of [CdL2] [NO3]2 · 2H2O
stretching vibrations (Table 2).
Electronic absorption spectral data of complexes in
dimethyl sulfoxide (DMSO) at room temperature that
are presented in experimental section. The absorption
bands below ca. 300 nm are practically identical and
Yield: 0.49 g (39.5%). Anal. Calcd. for
CdC22H24N4O8
Found: C, 42.72, H, 4.71, N, 8.92. 1H NMR (DMSOꢀ
d6, ppm): = 4.33 (H1, s, 4H), = 3.23 (H2, t, 2H,
J = 6.1), = 1.81 (H3, q, 4H, J = 7.6), = 1.44 (H4,
t, 4H, J = 7.4), = 3.41 (H2O), = 6.97–8.04 (m, 8H,
⋅
2H2O: C, 42.58, H, 4.56, N, 9.03.
δ
δ
δ
can be attributed to
π
π
* transitions in the benꢀ
δ
δ
zene ring and azomethine (–C=N) groups. The
absorption bands observed ca. the 300–380 nm range
δ
δ
ArꢀH),
(KBr,
(ionic
ΛM = 148
(DMSO): 278, 325, 378. Mass spectrum (m/z): [619,
1.1%, [CdL
): [619, 1.1%, [CdL2][NO3]2ꢀH]+].
δ
= 10.38 (s, 2H, HC=N). Selected IR data
are most probably due to the transitions of
imine groups [28, 29].
n
π
* of
ν
cm–1): 3354
ν
(H2O), 1646
ν
(C=N), 1384
The complexes are 1 : 2 electrolytes for Pb(II),
Cd(II) and Zn(II) complexes as shown by their molar
conductivities (ΛM) in DMSO at 10–3 M, which are in
ν
−), 513
ν
(Cd–O), 469
ν
(Cd–N).
NO3
–1
Ω
mol–1 cm2. UVꢀvis (λmax, nm)
the range 140–210
–1 cm2 mol–1 and 1 : 3 electrolytes
Ω
(m/z
for La(III) complexes as shown by their molar conꢀ
ductivities (ΛM) in DMSO at 10–3 M, which are in the
Ω
range 210–300
–1 cm2 mol–1 [30, 31].
RESULTS AND DISCUSSION
1
The H NMR spectra were run in DMSOꢀd6 and
gave the expected simple spectrum, indicating the
integrity of the complex in that solvent. The 1H NMR
spectrum of the complexes show a multiplet in the
range 6.90–8.15 ppm due to aromatic protons,
3.4 ppm due to H2O protons, around 1.99–4.32 ppm due
to CH2, OCH2 and OCH2Ph protons and 10.40 ppm
corresponding to the imine protons, but no signals
corresponding to the formyl or amine protons are
In the present work, we have synthesized Pb(II),
Zn(II), Cd(II) and La(III) complexes by template
reaction of 1,4ꢀbis(3ꢀaminopropoxy)butane or ( )ꢀ
transꢀ1,2ꢀdiaminocyclohexane with metal nitrate and
1,2ꢀbis(2ꢀformylphenyl)ethane in methanol, the [1 +
1] macrocyclic Schiffꢀbase complexes are formed as
the product. The macrocyclic complexes were characꢀ
terized by elemental analysis, UVꢀvis spectra, conducꢀ
tivity measurements, mass, 1H NMR and IR spectra.
The mass spectrum of complexes plays an important
role in confirming the monomeric [1 + 1] (dicarbonyl
1
present [31–33]. Also H NMR spectral data of the
complexes were given in experimental section (Fig. 2).
The mass spectra of the complexes play an imporꢀ
and diamine) nature of complexes. As the crystals were tant role in conforming the monomeric [1 + 1] (dicarꢀ
unsuitable for singleꢀcrystal Xꢀray structure determiꢀ bonyl and diamine) nature of the complexes. The fragꢀ
nation and are insoluble in most common solvents, ments observed in the mass spectrum of the complexes
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

SYNTHESIS AND SPECTRAL STUDIES
1405
Table 1
.
Physical characterization, analytical, molar conductance and mass data of the complexes
(Calcd.)Found
ΛM
(ohm1 cm2 mol–1)
Formula
Weight
Compound
MS/EI
Assigment
C, % H, % N, %
[PbL1][NO3]2
[ZnL1][NO3]2
⋅
H2O
(39.64) (4.57) (7.11)
40.11 4.73 6.93
(46.92) (5.11) (8.42)
47.07 5.22 8.58
H2O (38.19) (4.90) (8.57)
38.31 5.11 8.49
(45.09) (5.20) (8.09)
45.27 5.25 8.02
(36.92) (3.92) (7.83)
36.86 3.83 7.95
(46.07) (4.89) (9.77)
46.19 5.08 9.65
H2O (36.31) (3.85) (9.63)
36.42 4.01 9.52
(42.58) (4.56) (9.03)
45.72 4.71 8.92
194
181
259
152
186
171
272
148
787
665
817
692
715
573
727
620
569 [PbL1ꢀ(OCH2CH2OCH2)ꢀH]+
627 [[ZnL1][NO3]2]+
⋅
2H2O
[La(H2O)2L1][NO3]3
⋅
801 [[La(H2O)2L1][NO3]3]+
674 [[CdL1][NO3]2]+
[CdL1][NO3]2
[PbL2][NO3]2
[ZnL2][NO3]2
⋅
H2O
⋅
2H2O
569 [[PbL2] · H2O + 2H]+
542 [[ZnL2][NO3]2 + 3H]+
579 [LaL2ꢀ(OCH2)][NO3]ꢀ2H]+
619 [[CdL2][NO3]2ꢀH]+
⋅
2H2O
[LaL2(H2O)2][NO3]3
⋅
[CdL2][NO3]2
⋅
2H2O
Table 2
.
IR (cm–1) spectral data for the complexes
Compound (H2O) (C=N)
Ionic ν(NO–3 )
ν
ν
ν
(M–O)
ν
(M–N)
[PbL1][NO3]2
[ZnL1][NO3]2
[La(H2O)2L1][NO3]3
[CdL1][NO3]2
[PbL2][NO3]2
[ZnL2][NO3]2
[LaL2(H2O)2][NO3]3
[CdL2][NO3]2
2H2O
⋅
H2O
3349 s
3347 s
1645 m
1644 m
1642 m
1639 m
1638 m
1635 m
1634 m
1635 m
1384 m
1384 m
1384 m
1384 m
1383 m
1384 m
1383 m
1384 m
489 w
522 w
491 w
509 w
486 w
526 w
491 w
513 w
442 w
482 w
453 w
467 w
439 w
484 w
457 w
469 w
⋅
2H2O
⋅
H2O 3353 s
3362 s
⋅
H2O
⋅
2H2O
3356 s
⋅
2H2O
3351 s
⋅
H2O 3348 s
3354 s
⋅
m: medium, s: strong, w: weak.
are useful for characterization of the complexes [32–
34].The fragmentation mass spectra of the complexes
are described below:
[ZnL1][NO3]2
⋅
2H2O see Fig. 3.
H2O
[
La(H2O)2L1][NO3]3
⋅
–
[801, 7.8%,
[La(H2O)2L1][NO3]3]+], [755, 2.3%, [La(H2O)L1ꢀ
[PbL1][NO3]2
⋅
H2O – [569, 7.1%, [PbL1ꢀ
(CH2CH2)][NO3]3]+],
(CH2CH2CH2)
[LaL1(CH2CH2CH2)
[554,
2H]+],
2.9%,
[553,
[505,
[504,
[503,
[LaL1
9.0%,
5.5%,
28.5%,
77.1%,
(OCH2CH2OCH2)ꢀH]+], [505, 11.6%, [PbL1ꢀ
(CH2CH2OCH2CH2CH2CH2OCH2CH2)], [426, [L1ꢀ
(CH2) + H]+, 1.8%], [439, 100.0%, [L1 + H], [426, [L1ꢀ
(CH2) + H]+, 1.8%], [383, [L1ꢀ(CH2CH2CH2CH2)ꢀ
H]+, 5.1%], [356, [L1ꢀ(OCH2CH2CH2CH2CH2) +
+
+
H]+],
[LaL1(OCH2CH2CH2CH2O)]+],
[LaL1(OCH2CH2CH2CH2O)ꢀH]+],
[LaL1(OCH2CH2CH2CH2O)ꢀH]+], [440, 23.6%, [L1 +
+
+
H]+, 2.2%], 183 (C N
+
5.0%), 182 (C N
2H10,
2H], [439, 81.6%, [L1 + H], (206, 11.0%,
2H11,
12
12
[C10H24N2O2] + 2H]+), (205, 100.0%, [C10H24N2O2] +
+
37.0%), 181 (C N
2H10,
20.5%), 103 (C N 1.7%), 79
H5,
12
7
+
([C6H6]+)
.
H]+), 103 (C N 39.2%), (79, 21.0%, [C H + H]+).
H5,
7
6
6
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

1406
ILHAN et al.
(O CH2CH2)]]+], [303, 4.3%, [L2ꢀ(OCH2CH2)]ꢀ
H6
H5
H]+], [302, 1.0%, [L2ꢀ(OCH2CH2)]ꢀ2H]+], [301,
7.4%, [L2ꢀ(OCH2CH2)]ꢀ3H]+], [270, 2.4%,
[[C16H18N2O2]+], [269, 10.0%, [[C16H17N2O2]+],
[268, 1.6%, [[C16H16N2O2]+], [267, 9.3%,
[[C16H15N2O2]+], [265, 19.8%, [[C16H14N2O2]+],
[191, 7.6%, [[C13H21N]+], [189, 12.0%, [[C13H19N]+],
H4
H4
H3
H2
O
O
H3
H2
N
N
N
N
[[C13H17N]+],
[116,
5.8%,
O
O
O
O
[187,
20.0%,
[[C6H165N2]+], [115, 100.0%, [[C6H15N2]+], [98,
45.2%, [[C6H12N]+].
H1
H1
[LaL2(H2O)2][NO3]3
(OCH2)][NO3]2ꢀ2H]+],
⋅
H2O – [579, 1.7%, [LaL2ꢀ
[533, 1.9%,
[LaL2ꢀ
Fig. 2. Structure of the ligands.
(CH2)][NO3]ꢀ2H]+], [351, 2.0%, [L2]+3H]+], [350,
15.2%, [L2] + 2H]+], [349, 61.6%, [L2] + H]+], [218,
15.3%, [[C14H18O2]+], [217, 100.0%, [[C14H17O2]+],
CdL1][NO3]2
⋅
H2O
–
[674,
10.3%,
[Cd(L1][NO3]2]+], [613, 9.3%, [Cd(L1][NO3] + H]+],
[612, 21.7%, [Cd(L1][NO3]]+], [552, 3.7%, [Cd(L1) +
2H]+], [551, 10.7%, [Cd(L1) + H]+], [550, 37.3%,
[Cd(L1)]+], [522, 7.3%, [Cd(L1)ꢀ(CH2CH2)]+], [498,
4.1%, [Cd(L1)ꢀ(CH2CH2CH2CH2)]+], [467, 12.1%,
[Cd(L1)ꢀ(OCH2CH2CH2CH2O) + H]+], [440, 17.6%,
[L1 + 2H], [439, 100.0%, [L1 + H], (206, 14.9%,
[150, 37.4%, [[C9H14N2]+], [115, 31.5%,
+
[[C H N ]+], [101, C N
1.0%), [98, 12.4%,
H3,
7
6
15
2
[[C6H12N]+], (81, 2.1%, [C6H6 + 3H]+), (79, 27.4%,
[C6H6 + H]+).
[
CdL2][NO3]2
⋅
2H2O
–
[619, 1.1%,
[C10H24N2O2] + 2H]+), (205, 45.3%, [C10H24N2O2] +
[CdL2][NO3]2ꢀH]+], [457, 0.6%, [CdL2]ꢀ3H]+], [439,
0.6%, [CdL2ꢀ(CH2CH2)] + 3H]+], [406, 3.6%,
[CdL2ꢀ(OCH2CH2O)] + 2H]+], [405, 5.2%, [CdL2ꢀ
H]+), 103 (C7NH5 , 9.2%), (79, 11.2%, [C6H6 + H]+
.
+
[PbL2][NO3]2 2H2O – [569, 1.3%, [[PbL2]. H2O +
⋅
2H]+], [523, 4.8%, [[PbL2ꢀ(OCH2)]ꢀ2H]+], [426, 2.2%,
C14H7N2OPb]+], [350, 7.6%, [[L2] + 2H]+], [349, 31.9%,
[[L2] + H]+], [348, 44.0%, [[L2]]+], [347, 18.6%, [[L2]ꢀ
H]+], [346, 21.6%, [[L2]ꢀ2H]+], [332, 7.0%, [[L2ꢀ
(O)]]+], [331, 100.0%, [[L2ꢀ(O)]ꢀH]+], [330, 40.0%,
[[L2ꢀ(O)]ꢀ2H]+], [329, 45.6%, [[L2ꢀ(O)]ꢀ3H]+], [287,
10.2%, [[L2ꢀ(OCH2CH2)]ꢀH]+], [286, 12.5%, [[L2ꢀ
(OCH2CH2)]ꢀ2H]+], [285, 10.9%, [[L2ꢀ(OCH2CH2)]ꢀ
3H]+], [284, 6.5%, [[L2ꢀ(OCH2CH2)]ꢀ4H]+], [182,
97.6%, [[C10H16NO2]+], [181, 39.9%, [[C10H15NO2]+],
(OCH2CH2O)]
+
H]+], [404, 9.5%, [CdL2ꢀ
(OCH2CH2O)]+], [377, 5.4%, [[CdC16H13N2O2]+], [368,
25.6%,
[[CdC15H15N2O2]+],
[367,
100.0%,
[[CdC15H15N2O2]+], [351, 3.2%, [L2] + 3H]+], [350,
23.3%, [L2] + 2H]+], [349, 90.4%, [L2] + H]+], [318,
4.1%, [L2ꢀ(OCH2)]ꢀ3H]+], [115, 7.2%, [[C6H15N2]+],
[98, 2.7%, [[C6H12N]+].
The novel 6 Schiff base macrocyclic complexes
were prepared and characterized by elemental analyꢀ
ses, FTIR and UVꢀvis spectra, conductivity measureꢀ
[180, 2.6%, [[C10H14NO2]+], (78, 4.3%, [C6H6]+)
[ZnL2][NO3]2
.
1
ments, H NMR and mass spectra. Suggested strucꢀ
[
⋅
2H2O – [542, 5.8%, [ZnL2][NO3]2 + tures of the complexes were shown in Fig. 4. The comꢀ
3H]+], [514, 6.2%, [ZnL2ꢀ(CH2CH2)][NO3]2 + plexes have no clearly defined melting point and begin
3H]+], [513, 3.9%, [ZnL2ꢀ(CH2CH2)][NO3]2 + to decompose in the temperature range 250–350
°
C.
2H]+], [513, 13.4%, [ZnL2ꢀ(CH2CH2)][NO3]2 + The complexes are air stable, soluble in DMF, DMSO
H]+], [511, 4.8%, [ZnL2ꢀ(CH2CH2)][NO3]2]+], [510, and insoluble CHCl3, CH2Cl2 and less soluble MeOH,
15.8%, [ZnL2ꢀ(CH2CH2)][NO3]2ꢀ2H]+], [497, 9.6%, EtOH, CH3CN and the crystals were unsuitable for
[ZnL2ꢀ(OCH2CH2)][NO3]2 + H]+], [496, 6.1%, singleꢀcrystal Xꢀray structure determination. The
[ZnL2ꢀ(OCH2CH2)][NO3]2]+], [495, 24.2%, [ZnL2ꢀ binding mode of the ligand for the Pb(II) complexes
(OCH2CH2)][NO3]2ꢀH]+], [494, 8.1%, [ZnL2ꢀ behaves as hexadentate or tetradentate ligand with the
(OCH2CH2)][NO3]2ꢀ2H]+], [493, 24.1%, [ZnL2ꢀ lone electron pairs of azomethine nitrogen atoms and
(OCH2CH2)][NO3]2ꢀ3H]+], [492, 5.1%, [ZnL2ꢀ the lone electron pairs of four or two oxygen in ether
(OCH2CH2)][NO3]2ꢀ4H]+], [491, 18.5%, [ZnL2ꢀ groups. The binding mode of the ligand for the
(OCH2CH2)][NO3]2ꢀ5H]+], [477, 2.0%, [ZnL2ꢀ] La(III), Cd(II) and Zn(II) complexes behaves as a tetꢀ
[NO3]2]+], [475, 1.6%, [ZnL2]ꢀ[NO3]2]+], [413, 6.7%, radentate ligand with the lone electron pairs of azomeꢀ
[ZnL2]ꢀ2H]+], [368, 8.6%, [ZnL2ꢀ(OCH2CH2)]ꢀ thine nitrogen atoms and two atoms in ether groups.
2H]+], [367, 32.8%, [ZnL2ꢀ(OCH2CH2)]ꢀ2H]+], The long distance binding process can be favored for
[367, 32.8%, [ZnL2ꢀ(OCH2CH2)]ꢀ2H]+], [358, too large Pb(II) metal ions but not other metal ions
32.8%, [ZnL2ꢀ(OCH2CH2O)] + 2H]+], [357, 3.5%, due to having smaller ion size than Pb(II) metal ion.
[ZnL2ꢀ(OCH2CH2O)] + H]+], [356, 12.9%, [ZnL2ꢀ So its coordination is satisfied two H2O for La(III)
(OCH2CH2O)]]+],
[355,
3.3%,
[ZnL2ꢀ complex in the complexes of L1. Similar binding mode
(OCH2CH2O)]ꢀH]+], [350, 8.8%, [L2] + 2H]+], [349, was observed in literature for Pb(II), Zn(II) and
38.6%, [L2] + 2H]+], [337, 11.0%, [L2ꢀ(CH2)] + La(III) metal ion [31]. These results are clearly verify
3H]+], [318, 1.9%, [L2ꢀ(OCH2)]]+], [304, 1.3%, [L2ꢀ different binding mode of ligand in the case of the
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

SYNTHESIS AND SPECTRAL STUDIES
1407
+
+
+
O
O
O
O
O
O
N
N
N
N
N
N
[NO3]
[NO3]2
Zn
Zn
[NO3] –H
Zn
O
O
O
O
O
O
(m/z: 627, 1.3%)
(m/z: 564, 2.4%)
(m/z: 541, 1.2%)
+
+
+
O
O
O
O
O
O
N
N
N
N
N
N
–H
Zn
Zn
Zn
O
O
O
O
O
O
(m/z: 478, 3.4%)
(m/z: 503, 6.8%)
(m/z: 477, 10.6%)
+
+
+
O
O
O
O
O
N
N
N
N
N
N
–2H
Zn
–3H
Zn
–3H
Zn
O
O
O
O
O
O
(m/z: 462, 1.4%)
(m/z: 461, 5.8%)
(m/z: 458, 7.9%)
+
+
+4H
+
+
O
O
O
O
O
N
N
N
N
N
N
+3H
–3H
Zn
O
O
O
O
O
O
(m/z: 441, 7.6%)
(m/z: 442, 2.0%)
(m/z: 457, 28.3%)
+
+
O
O
O
O
O
O
N
N
N
N
N
N
+H
+H
+2H
O
O
O
O
O
O
(m/z: 440, 32.3%)
(m/z: 439, 100.0%)
(m/z: 413, 2.2%)
+
+
+
+
+
+H
O
O
N
–2H
N
O
O
+H
+H
–2H
N
N
(m/z: 79, 26.5%)
(m/z: 101, 6.2%)
(m/z: 103, 22.6%)
(m/z: 229, 51.4%)
(m/z: 205, 100.0%)
1
Fig. 3. The fragments observed in the mass spectrum of the [ZnL ] [NO ] · 2H O.
3 2
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

1408
ILHAN et al.
O
O
O
O
O
N
O
OH2
N
N
N
N
N
[NO3]2 ⋅ H2O
[NO3]2 ⋅ 2H2O
[NO3]3 ⋅ 2H2O
Pb
La
Zn
O
O
O
O
O
O
OH2
[PbL1][NO3]2 ⋅ H2O
[ZnL1][NO3]2 ⋅ 2H2O
[LaL1(H2O)2][NO3]3 ⋅ 2H2O
O
O
N
N
N
N
[NO3]2 ⋅ 2H2O
[NO3]2 ⋅ 2H2O
N
N
[NO3]2 ⋅ 2H2O
Pb
Zn
Cd
O
O
O
O
O
O
[CdL1][NO3]2 ⋅ 2H2O
[PbL2][NO3]2 ⋅ 2H2O
[ZnL2][NO3]2 ⋅ 2H2O
X
N
N
N
N
[NO3]3 ⋅ H2O
[NO3]2 ⋅ 2H2O
La
X
Cd
O
O
O
O
[LaL2(X)2][NO3]3 ⋅ H2O
[CdL2][NO3]2 ⋅ 2H2O
X : H2O
Fig. 4. Suggested structure of the complexes.
4. W. RadeckaꢀParyzek, V. Patroniak, and J. Lisowski,
Coord. Chem. Rev. 249, 2156 (2005).
5. S. Tamburini, P. A. Vigato, M. Gatos, et al., Inorg.
Chim. Acta 359, 183 (2006).
6. P. Guerrierro, P. A. Vigato, D. E. Fenton, and
P. C. Hellier, Acta Chem. Scand. 46, 1025 (1992).
7. H. Khanmohammadi, S. Amani, H. Lang, and T. Rueꢀ
Pb(II) metal ion [32]. Therefore, structure of the
Pb(II) complexes are different from structure of the
Zn(II) and La(III) complexes. Similar cases can be
seen in the literatures [31–34]. As a result Pb(II) metal
ion can bind six or four atoms and Zn(II) and Cd(II)
ions can bind four atoms and La(III) ions can bind six
atoms in the complexes. The Cd(II) and Zn(II) comꢀ
plexes probability show tetrahedral geometry and
La(III) complexes probability show octahedral geomꢀ
etry all the complexes, Pb(II) ions probability show
octahedral geometry in the L1 complex and tetrahedral
geometry in the L2 complex [31–33]. Absolute strucꢀ
ture of the complexes can be determined using Xꢀray
diffraction method. In this paper only suggested strucꢀ
ture of the complexes were given.
ffer, Inorg. Chim. Acta 360, 579(2007).
8. D. S. Kumar and V. Alexander, Polyhedron 18, 1561
(1999).
9. S. Tamburini, V. Vigato, M. Gatos, et al., Inorg. Chim.
Acta 359, 183 (2006).
10. M. E. S. Khal
il and K. A. Bashir, J. Coord. Chem. 55
(6), 681 (2002).
11. A. Chaudhary, N. Bansal, A. Gajraj, and R.V. Singh,
J. Inorg. Biochem. 96, 393(2003).
12. R. M. Izan, J. S. Brandshaw, S. A. Neilsen, et al.,
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