M. Montazerozohori et al. / Spectrochimica Acta Part A 81 (2011) 122–127
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solution (10 mL) of ethane-1,2-diamine (0.122 g, 2 mmol) as well as
stirring to a solution of (E)-2-methyl-3-phenylpropenal (0.584 g,
4 mmol) in absolute methanol (15 mL) within 20 min and fur-
thermore severely stirred for 5 h. After this time, the reaction
mixture was allowed to stay until the product being appeared
as yellowish white crystals. For purification of product, it was
filtered and washed with n-hexane as non-solvent and recrys-
tallized from dichlorometane/ethanol mixture to yield the ligand
in 66.6% (0.421 g) as yellowish white. The Schiff base is sol-
uble in common organic solvents but not in n-hexane and
n-heptane. %C22H24N2: calc. C, 83.50%; H, 7.64%; N, 8.85%;
found: C, 83.35%; H, 7.46%; N, 8.75%. Characteristic FT-IR and
UV–vis data were summarized in Table 1. 1H NMR (CHCl3):
7.87(d, 2H, J = 8.99 Hz), 7.24(m, 10H), 6.68(s, 2H), 3.74(s, 4H),
2.05(s, 6H) ppm. 13C NMR(DMSO-d6): 166.42, 138.43, 136.39,
136.20, 129.23, 128.39, 127.72, 60.81, 12.99 ppm. m.p. = 85 ◦C;
136.24, 129.24, 128.41, 127.76, 60.76, 12.97 ppm. m.p. = 145 ◦C
(dec.). ꢁM(DMSO) = 18.80 cm2 ꢂ−1 mol−1
.
- [CdLBr2]: Yield: 79%; white precipitate; %C22H24Br2CdN2: calc.
C, 44.89%; H, 4.11%; N, 4.76%; found: C, 44.8%; H, 4.2%; N,
4.9%. 1H NMR: 8.00(s, 2H), 7.41(d, 4H, J = 7.75 Hz), 7.38(t, 4H,
J = 7.90 Hz and J = 7.35 Hz), 7.28(t, 2H, J = 7.20 Hz), 6.86(s, 2H),
3.73(s, 4H), 2.02(s, 6H) ppm. 13C NMR: 166.45, 138.34, 136.28,
136.16, 129.26, 128.34, 127.66, 12.93, 60.70 ppm. m.p. = 205 ◦C
(dec.). ꢁM(DMSO) = 24.79 cm2 ꢂ−1 mol−1
- [CdLI2]: Yield: 79%; light yellow precipitate; %C22H24I2CdN2: calc.
C, 38.85%; H, 3.44%; N, 4.22%; found: C, 38.7%; H, 3.5%; N, 4.1%. 1
.
H
NMR: 8.01(s, 2H), 7.42(d, 4H, J = 7.30 Hz), 7.39(t, 4H, J = 7.85 Hz
and J = 7.25 Hz), 7.29(t, 2H, J = 7.15 Hz and J = 6.95 Hz), 6.88(s, 2H),
3.74(s, 4H), 2.03(s, 6H) ppm. 13C NMR: 166.48, 138.36, 136.31,
136.19, 129.18, 128.37, 127.69, 60.72, 12.96 ppm. m.p. = 197 ◦C
(dec.). ꢁM(CHCl3) = 0.375 cm2 ꢂ−1 mol−1
.
ꢁM(CHCl3) = 0.017 cm2 ꢂ−1 mol−1
.
- [CdL(SCN)2]: Yield: 73%; white precipitate; %C24H24S2CdN4: calc.
C, 52.89%; H, 4.44%; N, 10.28%; found: C, 53.1%; H, 4.6%; N,
10.1%. 1H NMR: 7.99(s, 2H), 7.41(d, 4H, J = 7.65 Hz), 7.38(t, 4H,
J = 7.75 Hz and J = 7.45 Hz), 7.28(t, 2H, J = 7.05 Hz and J = 6.95 Hz),
6.86(s, 2H), 3.73(s, 4H), 2.02(s, 6H) ppm. 13C NMR: 166.48, 138.37,
136.33, 136.21, 133.15, 129.19, 128.37, 127.70, 60.73, 12.96 ppm.
2.3. Synthesis of metal complexes
Zinc, cadmium and mercury complexes were synthesized by
gradually addition of the Schiff base ligand (0.5 mmol) in ethanol
(10 mL) to the respective metal halide, thiocynate or azide salts
(0.5 mmol) in absolute ethanol or methanol (5 mL) for 1–2 h
obtained as precipitate were filtered off, washed with ethanol
twice and dried under vacuum and recrystallized from chloroform
or dichloromethane/ethanol mixture (1:1). Then they were dried
under vacuum and kept in a desiccator over silica-gel. Character-
istic FT-IR and UV–vis data were summarized in Table 1 and other
physical and spectral data are as following:
m.p. = 199 ◦C (dec.). ꢁM(DMSO) = 61.62 cm2 ꢂ−1 mol−1
.
- [HgLCl2]: Yield: 87%; white precipitate, %C22H24Cl2HgN2; calc. C,
44.94%; H, 4.11%; N, 4.76%; found: C, 44.8%; H, 4.2%; N, 4.6%. 1H
NMR: 8.08(s, 2H), 7.42(d, 4H, J = 8.00 Hz), 7.39(t, 4H, J = 7.85 Hz
and J = 7.30 Hz), 7.30(t, 2H, J = 7.15 Hz and J = 6.80 Hz), 6.92(s, 2H),
3.76(s, 4H), 2.06(s, 6H) ppm. 13C NMR: 167.13, 139.16, 136.10,
135.99, 129.25, 128.41, 127.83, 60.72, 13.05 ppm. m.p. = 154 ◦C
(dec.). ꢁM(DMSO) = 8.23 cm2 ꢂ−1 mol−1
.
- [HgLBr2]: Yield: 79%; light yellow precipitate, %C22H24Br2HgN2;
calc. C, 39.04%; H, 3.57%; N, 4.14%; found: C, 39.2%; H, 3.7%; N, 4.2%.
1H NMR: 8.19(s, 2H), 7.44(d, 4H, J = 6.95 Hz), 7.41(t, 4H, J = 8.00 Hz
and J = 7.25 Hz), 7.32(t, 2H, J = 7.00 Hz and J = 6.90 Hz), 7.01(s, 2H),
3.79(s, 4H), 2.12(s, 6H) ppm. 13C NMR: 168.18, 140.47, 135.89,
135.42, 129.34, 128.46, 127.06, 60.63, 13.35 ppm. m.p. = 132 ◦C
- [ZnLCl2]: Yield: 87%; white precipitate, %C22H24Cl2ZnN2; calc. C,
58.36%; H, 5.34%; N, 6.19%; found: C, 57.06%; H, 5.24%; N, 6.28%.
1H NMR: 8.01(s, 2H), 7.41(d, 4H, J = 7.50 Hz), 7.38(t, 4H, J = 7.70 Hz
and J = 7.30 Hz), 7.29(t, 2H, J = 6.98 Hz and J = 6.55 Hz), 6.88(s, 2H),
3.74(s, 4H), 2.04(s, 6H) ppm. 13C NMR: 166.63, 138.53, 136.25,
136.17, 129.18, 128.36, 127.71, 60.70, 12.96 ppm. m.p. = 255 ◦C
(dec.). ꢁM(CHCl3) = 1.21 cm2 ꢂ−1 mol−1
.
- [HgLI2]: Yield: 85%; white precipitate %C22H24I2HgN2; calc. C,
34.28%; H, 3.14%; N, 3.63%; found: C, 34.14%; H, 3.23%; N, 3.51%.
1H NMR: 8.11(s, 2H), 7.43(d, 4H, J = 7.50 Hz), 7.40(t, 4H, J = 7.75 Hz
and J = 7.70 Hz), 7.31(t, 2H, J = 6.95 Hz and J = 6.85 Hz), 6.96(s, 2H),
3.76(s, 4H), 2.09(s, 6H) ppm; 13C NMR: 167.44, 139.52, 136.04,
135.85, 129.28, 128.43, 127.91, 60.73, 13.41 ppm. m.p. = 132 ◦C
(dec.). ꢁM(CHCl3) = 0.030 cm2 ꢂ−1 mol−1
.
- [ZnLBr2]: Yield: 84%; white precipitate; %C22H24Br2ZnN2: calc.
C, 48.78%; H, 4.47%; N, 5.17%; found: C, 48.5%; H, 4.6%; N, 5.3%.
1H NMR: 8.01(s, 2H), 7.41(d, 4H, J = 7.50 Hz), 7.38(t, 4H, J = 7.80 Hz
and J = 7.35 Hz), 7.29(t, 2H, J = 7.10 Hz and J = 6.85 Hz), 6.87(s, 2H),
3.74(s, 4H), 2.03(s, 6H) ppm. 13C NMR: 166.55, 129.18, 128.35,
136.18, 136.27, 138.44, 127.69, 60.70, 12.97 ppm. m.p. = 230 ◦C
(dec.). ꢃM(DMSO) = 4.21 cm2 ꢂ−1 M−1
.
- [HgL(N3)2]: Yield: 85%; cream precipitate, %C22H24HgN8; calc. C,
43.96%; H, 4.02%; N, 18.64%; found: C, 44.1%; H, 4.2%; N, 18.8%.
1H NMR: 8.02(s, 2H), 7.42(d, 4H, J = 7.15 Hz), 7.39(t, 4H, J = 7.90 Hz
and J = 7.30 Hz), 7.29(t, 2H, J = 7.10 Hz and J = 7.05 Hz), 6.88(s, 2H),
3.74(s, 4H), 2.04(s, 6H) ppm. 13C NMR: 166.54, 138.43, 136.32,
136.21, 129.20, 128.38, 127.71, 60.76, 12.96 ppm. m.p. = 120 ◦C.
(dec.). ꢁM(CHCl3) = 0.052 cm2 ꢂ−1 mol−1
.
- [ZnLI2]: Yield: 78%; white precipitate; %C22H24I2ZnN2: calc. C,
41.57%; H, 3.81%; N, 4.41%; found: C, 41.4%; H, 3.9%; N, 4.5%. 1H
NMR: 7.99(s, 2H), 7.39(d, 4H, J = 7.70 Hz), 7.36(t, 4H, J = 7.70 Hz
and J = 7.50 Hz), 7.27(t, 2H, J = 7.30 Hz and J = 6.65 Hz), 6.85(s, 2H),
3.71(s, 4H), 2.01(s, 6H) ppm. 13C NMR: 166.51, 138.42, 136.31,
136.19, 129.19, 128.38, 127.71, 60.73, 13.02 ppm. m.p. = 215 ◦C
ꢁM (DMSO) = 5.00 cm2 ꢂ−1 mol−1
.
(dec.). ꢁM(CHCl3) = 0.125 cm2 ꢂ−1 mol−1
.
- [ZnL(SCN)2]: Yield: 81%; white precipitate; %C24H24S2ZnN4: calc.
C, 57.65%; H, 4.76%; N, 11.13%; found: C, 57.8%; H, 4.8%; N,
11.2%. 1H NMR: 8.02(s, 2H), 7.42(d, 4H, J = 7.50 Hz), 7.39(t, 4H,
J = 7.80 Hz and J = 7.35 Hz), 7.29(t, 2H, J = 7.30 Hz and J = 6.80 Hz),
6.88(s, 2H), 3.74(s, 4H), 2.04(s, 6H) ppm. 13C NMR: 166.50, 138.38,
136.31, 136.19, 135.04, 129.18, 128.37, 127.69, 60.72, 12.95 ppm.
3. Results and discussion
3.1. Physical measurements and microanalysis data
The ratio of 1:1 for metal to ligand is well known from the
analytical data for all complexes. All complexes are soluble in
melting points of the ligand and complexes are at the range of
85–255 ◦C. The proposed general formula of complexes can be indi-
cated as MLX2 (M = Zn(II), Cd(II) and Hg(II); X = Cl−, Br−, I−, SCN−
and N3−) as shown in Fig. 1.
m.p. = 248 ◦C (dec.). ꢁM(CHCl3) = 0.063 cm2 ꢂ−1 mol−1
.
- [ZnL(N3)2]: Yield: 68%; yellow precipitate; %C22H24ZnN8: calc.
C, 56.72%; H, 5.19%; N, 24.05%; found: C, 56.5%; H, 5.3%; N,
24.2%. 1H NMR: 8.00(s, 2H), 7.40(d, 4H, J = 7.60 Hz), 7.37(t, 4H,
J = 7.65 Hz and J = 7.50 Hz), 7.28(t, 2H, J = 7.10 Hz), 6.86(s, 2H),
3.73(s, 4H), 2.03(s, 6H) ppm. 13C NMR: 166.68, 138.57, 136.32,