SYNTHESIS, SPECTRAL AND THERMAL STUDIES
579
ν
, cm–1): 2833 s (CH=N), 2855–3057 m
where X = I for Zn(II) and Cl for Hg(II) complexes.
IR (KBr;
(CH aromatic and aliphatic), 1628 s (C=N); 1H NMR
(CDCl3; , ppm): 3.70 (s., 6H), 3.71 (s., 6H), 3.79 (s.,
6H), 3.81 (s., 4H), 6.83 (d., 2H), 7.53 (d., 2H), 8.37
(s., 2H).
δ
EXPERIMENTAL
All reagents and solvents for synthesis and analysis
were commercially available and used as received
without further purifications. Infrared spectra were
recorded using KBr disks on a FTꢀIR PerkinElmer
spectrophotometer. Elemental analyses were carried
out using a Heraeus CHNꢀOꢀRapid analyzer, and
results agreed with calculated values. 1H NMR spectra
were measured on a BRUKER DRXꢀ500 AVANCE
spectrometer at 500 MHz for the Schiffꢀbase ligands
and their complexes. All chemical shifts are reported
Synthesis of II. To a stirring solution of the (234ꢀ
MeOꢀBa)2En ligand (0.2 mmol, in 5 ml of acetonitrile)
was added HgCl2 (0.2 mmol) in 20 ml methanol, and the
mixture was refluxed for 30 min in air. The solvent was
evaporator on a rotary evaporated at 40°C under reduced
pressure. The white solid residue was dissolved in 15 ml of
chloroform and filtered off. The filtrate was left at 273 K
for several days without disturbance of yielding microcꢀ
rystals of II that subsequently were filtered off and washed
with Et2O. The yield of colorless crystals was 75%.
in
analyses were done on a PerkinElmer TGA/DTA lab
system (Technology by SII) in nitrogen atmosphere
with a heating rate of 20°C/min from 35–700°C
δ units downfield from TMS. Thermogravimetric
I
For C22H28N2O6Cl2Hg
.
anal. calcd., %: C, 38.40;
H, 4.10;
H, 3.82;
N, 4.07.
N, 4.08.
Synthesis of (234ꢀMeOꢀBa)2En. A solution of 2,3,4ꢀ
trimethoxybenzaldehyde (3.92 g, 0.02 mol) in 25 ml
methanol was heated for 15 min at 50°C and then stirred
for about 15 min . To this stirring solution, a solution of
ethylenediamine (0.6 g, 0.01 mol) in 15 ml methanol was
added dropwise with constant stirring. The mixture was
heated at about 50°C for 1.5 h and then allowed to cool
overnight at 273 K. The resulting crude solid was collectꢀ
ed by filtration and dried at room temperature. Crystals
were grown by the slow evaporation technique at room
temperature in 25 ml of methanol as a solvent for 5 days.
At the period of supersaturation, tiny crystals were nucleꢀ
ated. They were allowed to grow to a maximum possible
dimension and then filtered. The yield of colorless crysꢀ
tals was 88%.
Found, %:
C, 37.66;
IR (KBr;
ν
, cm–1): 2835 s (CH=N), 2861–3035 m
(CH aromatic and aliphatic), 1625 s (C=N); 1H NMR
(CDCl3; δ, ppm): 3.73 (s., 6H), 3.77 (s., 6H), 3.82 (s.,
6H), 3.87 (s., 4H), 6.87 (d., 2H), 7.63 (d., 2H), 8.49
(s., 2H).
Xꢀray crystallography determination. Single crystals
suitable for the Xꢀray crystallographic abalysis of
obtained as colorless plates by slow evaporation of the
solvent methanol at 273 K (crystal size of : 0.10 0.18
0.24 mm). The intensity data for were collected at
173 K on a Stoe Mark IIꢀImage Plate Diffraction System
[11] equipped with a twoꢀcircle goniometer and using
I were
I
×
×
I
For C22H28N2O6
MoKαgraphite monochromated radiation (
Image plate distance was 130 mm, rotation scans 0°–
180° at φ = 0°, and 0°–62.0° at = 90°, step Δω = 1.3°,
exposures of 7 min per image, 2 range 1.76°–52.59°,
dmin max = 23.107–0.802 . The structure was solved by
λ= 0.71073 Å).
anal. calcd., %: C, 63.44;
H, 6.78;
H, 6.79;
N, 6.73.
N, 6.76.
ω
Found, %:
C, 63.49;
φ
θ
IR (KBr;
ν
, cm–1): 2834 s (CH=N), 2847–3047 m
–d
Å
(CH aromatic and aliphatic), 1637 s (C=N); 1H NMR
(CDCl3; δ, ppm): 3.81 (s., 6H), 3.83 (s., 6H), 3.87 (s.,
direct methods using the SHELXSꢀ97 programm [12].
The refinement and all further calculations were carried
out using SHELXLꢀ97 [12]. The H atoms were included
in calculated positions and treated as riding atoms using
SHELXL default parameters. The nonꢀH atoms were reꢀ
fined anisotropically, using weighted fullꢀmatrix leastꢀ
6H), 4.02 (s., 4H), 6.67 (d., 2H), 7.64 (d., 2H), 8.51
(s., 2H).
Synthesis of I. To a stirring solution of the (234ꢀ
MeOꢀBa)2En ligand (0.2 mmol, in 5 ml of chloroform)
was added ZnI2 (0.2 mmol) in 10 ml of methanol, and the
mixture was stirred for 10 min in air at room temperature
and then was left at 273 K for several days without disturꢀ
bance of yielding suitable crystals of I that subsequently
were filtered off and washed with Et2O. The yield of coꢀ
lorless crystals was 83%.
squares on F
2. An empirical absorption correction was
applied using the MULscanABS routine in PLATON
[13]. The molecule has crystallographic C2 symmetry
with the zinc(II) atom sitting on the 2ꢀfold rotation axis.
Crystallographic data and details of data collection and
structure refinement are given in Table 1.
Supplementary material for structure
I has been
For C22H28N2O6I2Zn
deposited with the Cambridge Crystallographic Data
Centre (no. 784976; deposit@ccdc.cam.ac.uk or
anal. calcd., %: C, 35.91;
Found, %: C, 35.96;
H, 3.83;
H, 3.60;
N, 3.80.
N, 3.81.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 8
2011
Khalaji
