SYNTHESIS, CHARACTERIZATION AND MASS
585
3.4. Characterization of [PbL2][NO3]2 . H2O
Yield: 0.27 (15.4%). Anal. Calcd. for
PbC30H42N4O12 H2O: C, 41.10, H, 5.02, N, 6.39.
Found: C, 41.46, H, 5.19, N, 6.33. 1H NMR (DMSOꢀ
d6, ppm): = 3.59 (H1, s, 4H), = 3.85 (H2, t, 4H,
J = 8.1), = 4.21 (H3, t, 4H, J = 7.6), = 3.56 (H4, t,
4H, J = 6.4), = 1.87 (H5, p, 4H, J = 4.3), 3.23 (H6,
t, 4H, J = 6.8), = 3.35 (H7, t, 4H, J = 7.3), = 1.42
(H7, t, 4H, J = 5.3), = 3.43 (H2O), = 7.01–8.10
(m, 8H, Ar–H), = 10.38 (s, 2H, HC=N). Selected
IR data (KBr, (H2O), 1647 (C=N),
cm–1): 3376
1384 (ionic (Pb–O), 436 (Pb–N).
−), 482
trioxaheptane
and
1,10ꢀbis(2ꢀformylphenyl)ꢀ
1,4,7,10ꢀtetraoxadecane, metal nitrate and 1,4ꢀbis(3ꢀ
aminopropoxy)butane in methanol, the [1 + 1] macꢀ
rocyclic Schiffꢀbase complexes are formed as the
product. The macrocyclic complexes were characterꢀ
ized by elemental analysis, UVꢀvis spectra, conductivꢀ
g
⋅
δ
δ
δ
δ
δ
1
ity measurements, mass, H NMR and IR spectra.
δ
δ
The mass spectrum of complexes plays an important
role in confirming the monomeric [1 + 1] (dicarbonyl
and diamine) nature of complexes. As the crystals were
unsuitable for singleꢀcrystal Xꢀray structure determiꢀ
nation and are insoluble in most common solvents,
including water, ethanol, ethyl acetate, and acetoniꢀ
trile.
δ
δ
δ
δ
δ
ν
ν
ν
ν
ν
ν
NO3
ΛM = 207 Ω–1 mol–1 cm2
.
UVꢀvis λmax nm)
(
,
(DMSO): 277, 324, 378. Mass spectrum (m/z): [628,
1.3%, [PbL2–(OCH2CH2OCH2CH2O)]+].
4.2. FTIR Spectra
3.5. Characterization of [ZnL2][NO3]2
Yield: 0.24 (16.3%). Anal Calcd. for
ZnC30H42N4O12 H2O: C, 48.98, H, 5.99, N, 7.62.
Found: C, 49.19, H, 6.11, N, 7.50. 1H NMR (DMSOꢀ
d6, ppm): = 3.88 (H1, t, 4H, J = 6.1), = 4.26 (H2,
t, 4H, J = 6.7), = 3.61 (H3, t, 4H, J = 5.6), = 1.96
(H4, p, 4H, J = 7.2), = 3.56 (H5, t, 4H, J = 5.4),
3.51 (H6, t, 4H, J = 4.8),
= 3.41 (H2O), = 6.93–8.08 (m, 8H, Ar–H),
10.38 (s, 2H, HC=N). Selected IR data (KBr,
3373 (H2O), 1649 (C=N), 1384 (ionic
(Zn–O), 481
(Zn–N). ΛM = 177 Ω–1 mol–1 cm2
⋅H2O
The characteristic infrared spectrum data was 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
g
⋅
δ
δ
δ
water molecule
complexes show a
absence of a
(C=O) peak at around 1700 cm–1 and
(NH2) peak at around 3300 cm–1 are indicative of
ν
(H2O) [20, 21]. The IR spectra of the
ν
δ
δ
(C=N) peak at 1685 cm–1 and the
δ
δ
=
=
ν
δ
= 1.33 (H7, t, 4H, J = 6.4),
ν
δ
δ
δ
Schiff’s base condensation. A strong band observed in
ν
cm–1):
the IR spectra of the complexes at ca.1645 cm–1 region
ν
ν
ν
−), 523
NO3
which is attributed to the ν(C=N) stretch, indicating
coordination of the azomethine nitrogen to metal [22,
23]. The presence of several bands in the region assoꢀ
ciated with nitrate vibrations clearly identifies these
species as containing nitrate groups. The absorptions of
ν
ν
.
UVꢀvis (λmax, nm) (DMSO): 279, 327, 382. Mass
spectrum (m/z): [735, 1.0%, [ZnL2][NO3]2
H2O+H]+].
⋅
the nitrate counterions, at ca. 1460–1452 (ν5), 1300 (ν1
)
and 1040 (ν2) cm–1, suggest the presence 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 the bands between
3.6. Characterization of [LaL2][NO3]3
⋅ 2H2O
Yield: 0.32
g
(18.0%). Anal. Calcd. for
LaC30H42N5O16 . 2H2O): C, 40.54, H, 5.18, N, 7.88.
Found: C, 41.12, H, 5.31, N, 7.73. 1H NMR (DMSOꢀ
2965–2855 cm–1 due to
ν(Alph.–CH) groups. Concluꢀ
sive evidence of the bonding is also shown by the
observation that new bands in the IR spectra of the comꢀ
plexes appear at 525–485 cm–1 and 481–435 cm–1
d6,
t, 4H, J = 7.3),
(H4, p, 4H, J = 7.4),
3.54 (H6, t, 4H, J = 8.1),
= 3.41 (H2O), = 7.00–8.04 (m, 8H, Ar–H),
10.40 (s, 2H, HC=N). Selected IR data (KBr,
3369 (H2O), 1644 (C=N), 1384 (ionic
(La–O), 462
(La–N). ΛM = 262 Ωꢀ1 mol–1 cm2. UVꢀ
δ
ppm):
δ
= 3.81 (H1, t, 4H, J = 6.7),
= 3.62 (H3, t, 4H, J = 6.2),
= 3.57 (H5, t, 4H, J = 6.6),
δ
= 4.28 (H2,
δ
δ
= 1.96
δ
δ
=
=
assigned to
ν(M–O) and ν(M–N) stretching vibraꢀ
δ
= 1.35 (H7, t, 4H, J = 5.8),
tions [26, 27].
δ
δ
δ
ν
cm–1):
−), 495
4.3. Electronic Spectra
ν
ν
ν
NO3
ν
ν
Electronic absorption spectral data of complexes in
dimethylsulfoxide (DMSO) at room temperature that
are presented in experimental section. The absorption
bands below ca. 300 nm are practically identical and
vis (λmax, nm) (DMSO): 277, 326, 376. Mass spectrum
(m/z): [852, 1.1%, [LaL2][NO3]3]+].
can be attributed to π−π* transitions in the benzene
ring and azomethine (–C=N) groups. The absorption
bands observed ca. the 300–330 nm range are most
4. RESULT AND DISCUSSION
4.1. Macrocyclic Schiff Base Complexes
probably due to the transitions of n–π* of imine
In this work, I have found that in the reaction
between synthesis of 1,7ꢀbis(2ꢀformylphenyl)ꢀ1,4,7ꢀ groups [28, 29].
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010