M.K. Rofouei et al. / Polyhedron 44 (2012) 138–142
139
Perkin–Elmer RXI spectrometer using KBr disks. Elemental analysis
was carried out using a Perkin–Elmer 2400(II) CHNS/O analyzer.
Melting points were measured on a Barnstead Electrothermal
9200 apparatus.
2.1.3. Synthesis of [HgII(EtOPhNNNPhCN)2], [Hg(L1)2], (2)
The complex was prepared by mixing 0.27 g (1 mmol) of [1-
(2-ethoxyphenyl)-3-(2-cyanophenyl)triazene) in 10 ml of anhy-
drous methanol with 0.27 g (1 mmol) of mercury(II) nitrate in
10 ml of anhydrous methanol. After being mixed for an hour, a
yellow precipitate was obtained. The resultant precipitate after
filtration and washing was dissolved in THF. Yellow needle-like
crystals suitable for X-ray analysis of the complex (2) were ob-
tained by slow evaporation of the solvent in 2 weeks.
2.1.1. Synthesis of [(EtOPhNHNNPhCN)], [HL1]
A 100 ml flask was charged with 10 g of ice and 15 ml of water
and then cooled to 273 K in an ice-bath. To this was added 2 mmol
(0.24 g) of 2-aminobenzonitrile and 2 mmol of hydrochloric acid
(36.5%) and 2 ml of water. To this solution was then added a solu-
tion containing NaNO2 (0.32 g) in 3 ml of water during a 15 min
period. The pH of the solution was then adjusted at 6 by adding a
solution containing 1 g of sodium acetate in 10 ml of water. After
mixing for 15 min, the obtained solution was added to a solution
of 2 mmol (0.26 ml) of o-phenetidine and 2 ml of methanol and
4 ml of water. After mixing for 24 h, the yellow-orange precipitate
was filtered off and dried. Our attempt to crystallize this compound
C
30H26HgN8O2 (731.18); m.p.: 219–221 °C. IR (KBr): m
(cmÀ1):
3069, 2977 , 2220, 1589, 1494, 1477, 1372, 1333, 1291, 1275,
1218, 1161, 1120, 1038, 918, 743, 734, 672. 1H NMR (300 MHz,
d6-DMSO): 1.16 (3H, CH3), 4.10 (2H, CH2), 7.00–7.81 (8H, aro-
matic). 13C NMR 300 MHz, d6-DMSO): 14.0, 64.5, 104.8–
151.4 ppm. Elemental Anal. calc. for C30H26HgN8O2: C, 49.31; H,
3.56; N, 15.34. Found: C, 49.60; H, 3.38; N, 15.26%.
2.1.4. Synthesis of [HgII(EtOPhNNNPhCl)2], [Hg(L2)2], (3)
was unsuccessful. m.p.: 121–123 °C. IR (KBr): m
(cmÀ1): 3331, 2223,
To a yellow solution prepared by dissolving 0.29 g (1 mmol) of 1-
(2-ethoxyphenyl)-3-(2-chlorophenyl)triazene in 40 ml of anhy-
drous methanol, 0.16 g (0.5 mmol) of mercury(II) nitrate dissolved
in 5 ml of anhydrous methanol were added. After 1/2 h stirring, an
orange precipitate was formed. It was then filtered off, washed with
methanol and dried in vacuum. The solid was dissolved in 20 ml THF.
Orange-red plate like crystals suitable for X-ray analysis of the com-
plex, were obtained by slow evaporation of the solvent within a
1602, 1513, 1478, 1470, 1437 , 1313, 1275, 1231, 1119, 1040, 927,
770, 735, 603. 1H NMR (300 MHz, d6-DMSO): 1.38 (3H, CH3), 4.13
(2H, CH2), 6.90–7.85 (8H, aromatic), 12 (1H, NH). 13C NMR
(300 MHz, d6-DMSO): 14.5, 64.0, 102.2–145.5 ppm. Elemental Anal.
calc. for C15H14N4O: C, 67.66; H, 5.26; N, 21.05. Found: C, 67.38; H,
4.26; N, 20.65%.
week. IR (KBr):
m
(cmÀ1): 2881, 1584, 1493, 1470, 1456, 1386,
2.1.2. Synthesis of [(EtOPhNHNNPhCl)] [HL2], (1)
1286, 1263, 1235, 121, 1196, 1121, 1035, 918, 759, 741, 735. 1H
NMR (300 MHz, d6-DMSO): 1.17 (3H, CH3), 4.06 (2H, CH2), 6.99–
7.73 (8H, aromatic). 13C NMR (300 MHz, d6-DMSO): 14.1, 64.3,
113.0–150.5 ppm. Elemental Anal. calc. for C28H26Cl2HgN6O2: C,
44.84; H, 3.49; N, 11.2. Found: C, 45.18; H, 3.51; N, 11.12%.
This ligand was also prepared by the same method as described
above with this difference that o-chlorobenzenamine (0.1 mol,
10.54 ml) was used as starting material. Also, recrystallization
was performed by n-hexane. m.p.: 73–75 °C. IR (KBr):
m
(cmÀ1):
3336, 3067, 1600, 1530, 1467, 1437, 1410 , 1306, 1259, 1212,
1119, 1045, 1035, 746, 732, 719. 1H NMR (300 MHz, d6-DMSO):
1.38 (3H, CH3), 4.12 (2H, CH2), 6.92–7.61 (8H, aromatic), 11.72
(1H, NH). 13C NMR (300 MHz, d6-DMSO): 14.7, 64.1, 112.8–
146.5 ppm. Elemental Anal. calc. for C14H14N3OCl: C, 60.98; H,
5.12; N, 15.24. Found: C, 61.04; H, 5.0; N, 15.29%.
3. Crystallography
Crystallography measurements were made using a Bruker
APEX2 CCD diffractometer for compounds (2) and (3), and also
Table 1
Crystal data for the compounds (1)–(3).
1
2
3
Empirical formula
Formula weight
T (K)
C
14H14ClN3O
C30H26HgN8O2
731.18
293
C28H26Cl2HgN6O2
750.04
293
275.73
298
k (Å)
0.71073
monoclinic
P21/c
0.71073
triclinic
P1
0.71073
monoclinic
C2/c
Crystal system
Space group
Unit cell dimensions
a (Å)
b (Å)
c (Å)
ꢀ
14.688 (3)
4.4064 (9)
22.337 (8)
7.9472 (3)
8.6812 (3)
20.7136 (7)
22.497 (4)
9.049 (2)
14.746 (3)
a
(Å)
91.245 (2)
b (Å)
111.46 (2)
92.970 (2)
108.89 (2)
c
(Å)
91.811 (2)
1426.03 (9)
V (Å3)
1345.5 (6)
2840.2 (10)
Z
4
2
4
Dcalc (Mg mÀ3
)
1.361
0.279
1.703
4.439
1.754
5.646
Absorption coefficient (mmÀ1
)
F(000)
576
716
1464
h Range for data collection (°)
1.96–29.22
0.98–30.06
2.68–30.30
Index ranges
À20 6 h 6 20,–6 6 k 6 5,
À 28 6 l 6 30
13923/3595 (0.0905)
Full-matrix least-squares on F2
3595 / 0 / 177
1.134
À11 6 h 6 11,–12 6 k 6 12,
À 29 6 l 6 29
57106/8309 (0.052)
Full-matrix least-squares on F2
8309 / 0 / 370
1.14
À31 6 h 6 31,–12 6 k 6 12,
À 20 6 l 6 20
58699/4223 (0.031)
Full-matrix least-squares on F2
4223 / 0 / 177
1.019
Reflections collected/unique (Rint
Refinement method
)
Data/restraints/parameters
Goodness-of-fit on F2
Final R[I > 2
R indices (all data)
Largest differences in peak and hole
(e AÀ3
r
(I)]
R1 = 0.0742, wR2 = 0.1335
R1 = 0.1346, wR2 = 0.1553
0.231 and À0.184
R1 = 0.0654, wR2 = 0.1665
R1 = 0.0748, wR2 = 0.1702
2.89 and À4.32
R1 = 0.0242, wR2 = 0.0718
R1 = 0.0273, wR2 = 0.0737
0.89 and À1.36
)