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M. Ikram et al. / Thermochimica Acta 555 (2013) 72–80
831(s), 759(s), 696(s) cm−1
,
ꢀmax = 890 nm (ε = 16.6 M−1 cm−1
,
with n-hexane three times. The product was recrystalized from
methanol as yellow needles.
2
2A2g → B1g).
2.8. 2-{(E)-[(4-Chlorophenyl)imino]methyl}phenol (CIMP)
2.13. Bis(2-{(E)-[(4-chlorophenyl)imino]methyl}
phenolate)copper(II) (3)
Yield; 75%, m.p. 93–95 ◦C elemental analysis, C13H10ClNO, Calc.
C: 67.39%, H: 4.35%, N: 6.05%, Exp. C: 67.90%, H: 4.30%, N:
6.57%, IR analysis: 3400(bd), 1683(s), 1608(s), 1485(s), 1456(s),
1394(w), 1271(s), 1149(s), 1010(s), 908(w), 835(s), 813(s), 754(s),
Yield;
68%,
m.p.
219–220 ◦C
elemental
analysis,
C
26H18Cl2CuN2O2, Calc. C: 59.49%, H: 3.46%, Cu: 12.11%, N:
5.34%, MS-ES+: m/z (%) = 545.9939 (100%) [C26H18CuCl2N2O2+Na],
IR analysis: 1598(s), 1573(s), 1519(s), 1489(s), 1431(s), 1390(s),
1348(s), 1321(s), 1300(s), 1249(s), 1211(w), 1170(s), 1147(s),
1126(s), 1093(s), 1029(s), 1006(s), 975(s), 923(s), 852(s), 827(s),
698(s), 630(w) cm−1
,
1H NMR (300.13 MHz, CDCl3, 303k) ı = 6.9
3
3
(d, JHH = 7.2 Hz, 1H, H12), 7.04 (d, JHH = 7.23 Hz, 1H, H15), 7.1 (d,
3JHH = 7.56 Hz, 1H, H14 and H13), 7.4 (d, 3JHH = 7.01 Hz, 1H, H3 and
3
756(s), 696(s), 610(s) cm−1, ꢀmax = 690 nm (ε = 220.6 M−1 cm−1
,
H5), 7.5 (d, JHH = 7.25 Hz, 1H, H2 andH6), 8.6 (s, Ar HC N), 13.0
1
(s, OH), 13C{ H} NMR (75.47 MHz, CDCl3, 303k), 117.3 (CH, C15),
dZ → dX
2
2 ).
2
−Y
119.0 (CH, C13), 119.2 (CH, C14), 122.4 (CH, C2 and C6), 129.5 (CH,
C3 and C5), 132.4 (CH, C12), 133.48 (C, C4), 147.0 (C, C1), 161.1 (C,
C11), 162.9 (CH, Ar HC N).
2.14. Bis(2-{(E)-[(4-chlorophenyl)imino]methyl}
phenolate)zinc(II) (4)
2.9. 2-{(E)-[(4-bromophenyl)imino]methyl}phenol (BIMP)
Yield;
55%,
m.p.
278–280 ◦C
elemental
analysis,
C
26H18Cl2N2O2Zn, Calc. C: 59.28%, H: 3.44%, N: 5.32%, Zn:
Yield; 80%, m.p. 90–92 ◦C elemental analysis, C13H10BrNO, Calc.
C: 56.55%, H: 3.65%, N: 5.07%, IR analysis: 3400(bd), 1606(s),
1568(s), 1481(s), 1409(s), 1359(s), 1280(s), 1184(s), 1151(s),
12.42%, MS-ES+: m/z (%) = 524.0063 (80%) [C26H18Cl2N2O2Zn+],
IR analysis: 1598(s), 1581(s), 1521(s), 1460(s), 1435(s), 1394(s),
1348(s), 1325(s), 1249(s), 1170(s), 1147(s), 1093(s), 1029(s),
1107(s), 1006(s), 983(s), 910(s), 852(s), 752(s), 678(s) cm−1 1H
.
1006(s), 923(s), 827(s), 786(s), 756(s), 698(s), 590(s) cm−1
.
NMR (300.13 MHz, CDCl3, 303k) ı = 6.9 (d, 3JHH = 7.01 Hz, 1H, H12),
3
3
7.03 (d, JHH = 7.2 Hz, 1H, H15), 7.1 (d, JHH = 7.34 Hz, 1H, H14 and
2.15. Bis(2-{(E)-[(4-bromophenyl)imino]methyl}
phenolate)nickel(II) (5)
3
3
H13), 7.4 (d, JHH = 6.8 Hz, 1H, H3 and H5), 7.5 (d, JHH = 7.9 Hz,
1H, H2 andH6), 8.6 (s, Ar HC N), 13.0 (s, OH), 13C{ H} NMR
1
(75.47 MHz, CDCl3, 303k), 117.3 (CH, C3 and C5), (CH, C15), 119.0
(CH, C13), 119.2 (CH, C14), 122.8 (CH, C2 and C6), 132.4 (CH, C12),
133.5 (C, C4), 147.4 (C, C1), 161.1 (C, C11), 162.9 (CH, Ar HC N).
Yield;
83%,
m.p.
100–102 ◦C
elemental
analysis,
C
26H18Br2N2NiO2, Calc. C: 51.28%, H: 2.98%, N: 4.60%, Ni:
9.64%, m/z (%) = 605.5830 (100%) [C26H18Cl2N2NiO2+], IR anal-
ysis: 1611(s), 1531(s), 1466(s), 1444(s), 1418(s), 1349(s), 1330(s),
1258(s), 1220(s), 1188(s), 1142(s), 1142(s), 1116(s), 1023(w),
976(s), 938(s), 901(s), 862(w), 812(s), 806(s), 759(s), 748(s),
2.10. Synthesis of complexes
10 mmol of the Schiff base ligand in 10 cm3 of dried methano-
lic solution was added to the dehydrated methanolic solution of
0.4 mmol metal salts and stirred the mixture for 3–6 h. Partial dehy-
dration of the metal salts was achieved by keeping the metal salts
in oven at 105 ◦C for 3 h. These metal salts were dissolved in 10 cm3
dried methanol and excess dimethoxy propane was added to it
to achieve the complete dehydration. On mixing the metal salt
solution with ligand solutions, the complexes either precipitated
instantaneously otherwise obtained by concentrating the solutions
using rotary evaporator. The product was washed with 10% copious
methanol containing n-hexane solution.
721(s), 698(s), 667(s) cm−1
,
ꢀmax = 890 nm (ε = 16.6 M−1 cm−1
,
1
1A1g → A2g).
2.16. Bis(2-{(E)-[(4-bromophenyl)imino]methyl}
phenolate)cobalt(II) (6)
Yield;
75%,
m.p.
230–232 ◦C
elemental
analysis,
C26H18Br2CoN2O2, Calc. C: 51.26%, H: 2.98%, Co: 9.67%, N:
4.60%, m/z (%) = 606.7541 (100%) [C26H18Cl2CoN2O2+], IR analysis:
1683(w), 1653(s), 1604(s), 1533(s), 1483(w), 1463(s), 1446(s),
1379(s), 1348(s), 1327(s), 1253, 1180(s), 1149(s), 1072(s), 1010(s),
925(s), 856(s), 831(s), 761(s), 711(s), 678(s) cm−1, ꢀmax = 790 nm
(ε = 16.6 M−1 cm−1
,
2A2g → B1g).
2
2.11. Bis(2-{(E)-[(4-chlorophenyl)imino]methyl}
phenolate)nickel(II) (1)
2.17. Bis(2-{(E)-[(4-bromophenyl)imino]methyl}
phenolate)copper(II) (7)
Yield;
55%,
m.p.
248–250 ◦C
elemental
analysis,
C
26H18Cl2N2NiO2, Calc. C: 60.05%, H: 3.49%, N: 5.39% Ni: 11.29%,
MS-ES+: m/z (%) = 540.9997 (100%) [C26H18Cl2N2NiO2+Na], IR
analysis: 3303(bd), 1611(s), 1531(s), 1466(s), 1444(s),1418(s),
1349(s), 1330(s), 1258(s), 1220(s), 1188(s), 1142(s), 1142(s),
1116(s), 1023(w), 976(s), 938(s), 901(s), 862(w), 812(s), 806(s),
Yield;
71%,
m.p.
276–278 ◦C
elemental
analysis,
C26H18Br2CuN2O2, Calc. C: 50.88%, H: 2.96%, Cu: 10.35%, N:
4.56%, m/z (%) = 611.1259 (90%) [C26H18Br2CuN2O2+H]+, IR
analysis: 1597(s), 1570(s), 1521(s), 1490(s), 1460(s), 1429(s),
1388(s), 1348(s), 1321(s), 1249(s), 1209(s), 1170(s), 1147(s),
1126(s), 1078(s), 1029(s), 1002(s), 975(s), 925(s), 852(s), 823(s),
759(s), 748(s), 721(s), 698(s), 667(s) cm−1
,
ꢀmax = 710 nm
(ε = 27.7 M−1 cm−1
,
1A1g → A2g).
1
786(s), 756(s), 677(s) cm−1. ꢀmax = 690 nm (ε = 220.6 M−1 cm−1
,
2.12. Bis(2-{(E)-[(4-chlorophenyl)imino]methyl}
phenolate)cobalt(II) (2)
dZ → dX
2
2 ).
2
−Y
2.18. Bis(2-{(E)-[(4-bromophenyl)imino]methyl}
phenolate)zinc(II) (8)
Yield;
75%,
m.p.
270–272 ◦C
elemental
analysis,
C
26H18Cl2CoN2O2, Calc. C: 60.02%, H: 3.49%, Co: 11.33% N: 5.38%,
MS-ES+: m/z (%) = 519.0075 (100%) [C26H18Cl2CoN2O2+], IR analy-
sis: 1606(s), 1537(s), 1485(s), 1463(s), 1440(s), 1379(s), 1325(s),
1178(s), 1149(s), 1126(s), 1089(s), 1012(s), 979(s), 925(s), 856(s),
Yield;
45%,
m.p.
278–280 ◦C
elemental
analysis,
C26H18Br2N2O2Zn, Calc. C: 50.72%, H: 2.95%, N: 4.55%, Zn: 10.62%,
m/z (%) = 611.3404 (100%) [C26H18Br2N2O2Zn+], IR analysis: