2950 Choong et al.
Asian J. Chem.
separated by filtration and kept in a bottle. After few days,
transparent solids (0.73 g, 66.7 % yield) were collected. m.p.:
180.3-182.9 °C. Analysis for C16H12N2O8Cl2Sn1: C, 34.08; H,
1.93; N, 5.11 %. Calculated for C16H12N2O8Cl2Sn1 C, 34.95;
H, 2.20; N, 5.09 %. FTIR (KBr disc, cm-1): ν(C-H) aromatic
3048, ν(C-H) saturated 2931; ν(COO)as 1717; ν(COO)s 1349,
∆ν = 368; ν(NO2) 1528, ν(O-Sn-O) 624, ν(Sn-C) 544, ν(Sn-
O) 492. 1H NMR (ppm) (CDCl3): δ: benzene protons 8.16 (d,
8.7 Hz, 2H); 8.20 (dd, 2.3 Hz, 6.4 Hz, 2H); 8.36 (d, 1.8 Hz,
solution was isolated by filtration and kept in a bottle. After
few days, transparent crystals (0.71 g, 69.5 % yield) were
collected. m.p.: 115.6-116.6 °C.Analysis for C26H22N1O5ClSn:
C, 53.45; H, 3.74; N, 2.33 %. Calculated for C26H22N1O5Cl1Sn1:
C, 53.60; H, 3.81; N, 2.40 %. FTIR (KBr disc, cm-1): ν(C-H)
aromatic 3072, 3052; ν(C-H) saturated 2979, ν(COO)as 1618,
ν(COO)s 1345, ∆ν = 273; ν(NO2) 1522, ν(Sn-O) 457. 1H NMR
(ppm) (d6 DMSO): δ: phenyl protons 7.41-7.48 (m, 9H); 7.86-
7.88 (m, 6H); benzene 7.60 (d, 8.5 Hz, 1H); 8.12 (dd, 2.3 Hz,
6.6 Hz, 1H); 8.19 (d, 2.3 Hz, 1H); CH3OH 3.18 (d, 4.8 Hz,
3H), 4.15 (q, 5.0 Hz, 1H). 13C NMR (ppm) (d6-DMSO): δ:
phenyl carbons Cipso 142.73 (798.0 Hz), Cortho 136.26 (45.4
Hz), Cmeta 128.44 (69.5 Hz), Cpara 129.11; benzene 122.24,
124.92, 129.44, 130.25, 131.00, 147.67; CH3OH 48.72; COO
167.61. 119Sn-NMR (ppm) (d6-DMSO): δ: -261.65.
13
2H); methyl 1.30 (s, 6H), 2J(119Sn-1H) = 81.1 Hz. C NMR
(ppm) (CDCl3): δ: benzene carbons 121.48, 126.30, 133.06,
134.52, 135.71, 149.87; methyl 5.48, COO 170.42. 119Sn NMR
(ppm) (CDCl3): δ: -97.20.
Preparation of (2-Cl-4-NO2-C6H3COO)2(C4H9)2Sn (2):
Complex 2 was obtained by heating under reflux a 1:2 molar
mixture of dibutyltin(IV) oxide (0.50 g, 2 mmole) and 2-
chloro-4-nitrobenzoic acid (0.81 g, 4 mmole) in ethanol
(50 mL) for 4 h. A clear colourless transparent solution was
separated by filtration and kept in a bottle. After few days,
transparent solids (0.86 g, 67.8 % yield) were collected. m.p.:
115.6-116.6 °C. Analysis for C22H24N2O8Cl2Sn: C, 41.98; H,
4.06; N, 4.43 %. Calculated for C22H24N2O8Cl2Sn1: C, 41.67;
H, 3.82; N, 4.42 %. FTIR (KBr disc, cm-1): ν(C-H) aromatic
3082, ν(C-H) saturated 2961, 2934, 2868; ν(COO)as 1602;
ν(COO)s 1347, ∆ν = 255; ν(NO2) 1554, ν(O-Sn-O) 640, ν(Sn-
2-Chloro-4-nitrobenzoic acid, HL: The parent acid, 2-
chloro-4-nitrobenzoic acid, HL was purchased from Acros
Organics and used without any further purification. FTIR (KBr
disc, cm-1): selected data: ν(OH) 2823-2577, ν(COO)as 1708,
1
ν(COO)s 1356, ∆ν = 353. H NMR (ppm) (d6-DMSO): δ:
benzene protons 7.98 (d, 8.7 Hz, 1H); 8.23 (dd, 1.8 Hz, 4.1
Hz, 1H); 8.33 (d, 2.3 Hz, 1H). 13C NMR (ppm) (d6-DMSO):
δ: benzene carbons 122.84, 125.82, 131.99, 132.63, 138.11,
149.42; COO 166.26.
Preliminary in vitro antibacterial screening activity:
The synthesized complexes 1-4 and acid, 2-chloro-4-nitro-
benzoic acid were screened for their in vitro antibacterial activity
against two Gram-negative [Escherichia coli (ATCC 25922)
and Pseudomonas aeruginosa (ATCC 27853)] and two Gram-
positive [Bacillus subtilis (ATCC 38583) and Staphylococcus
aureus (ATCC 25923)] bacterial strains by Inhibition Zone
Method using paper disc diffusion method16-17. The seeded agar
(nutrient agar medium) was prepared by cooling the molten
agar to 40 °C and then adding bacterial inoculums containing
approximately 1 × 104-108 colony forming units (CFU)/mL.
The bacterial inoculums were spread on the plate containing
agar medium and even coverage was ensured before the agar
solidified. The complexes were dissolved in DMSO to prepare
1.0 mg/mL concentration. Later, small filter paper discs (6 mm)
containing 1.0 mg/mL of the samples were laid on the growth
medium. The plates were incubated immediately at 37 °C for
20-24 h. The activity was determined by measuring the diameter
of the inhibition zone (in mm).
1
C) 520, ν(Sn-O) 485. H NMR (ppm) (CDCl3): δ: benzene
protons 8.13 (d, 8.3 Hz, 2H); 8.19 (dd, 1.8 Hz, 6.4 Hz, 2H);
8.33 (d, 2.3 Hz, 2H); butyl, CH3 0.95 (t, 7.4 Hz, 6H), CH2
1.48 (sx, 7.3 Hz, 4H); CH2 1.84 (qn, 7.3 Hz, 4H); CH2 1.98 (t,
8.7 Hz, 4H). 13C NMR (ppm) (CDCl3): δ: benzene carbons
121.53, 126.09, 132.75, 135.09, 136.02, 149.59; butyl 13.63,
26.41, 26.75, 26.90; COO 173.30. 119Sn-NMR (ppm) (CDCl3):
δ: -123.40.
Preparation of [{2-Cl-4-NO2-C6H3COO(C4H9)2Sn}2O]2
(3): Complex 3 was obtained by heating under reflux a 1:1
molar mixture of dibutyltin(IV) oxide (0.50 g, 2 mmole) and
2-chloro-4-nitrobenzoic acid (0.41 g, 2 mmole). The reaction
was carried out in a mixture of ethanol (60 mL) for 3 h. A
clear transparent solution was isolated by filtration and kept
in a bottle. After few days, colourless crystals (0.73 g, 83.7 %
yield) were collected. m.p.: 175.4-176.5 °C. Analysis for
C60H84N4O18Cl4Sn4: C, 41.22; H, 4.47; N, 3.20 %. Calculated
for C60H84N4O18Cl4Sn4: C, 40.81; H, 4.79; N, 3.17 %. FTIR
(KBr disc, cm-1): ν(C-H) aromatic 3100, 3065; ν(C-H) satu-
rated 2960, 2928, 2861; ν(COO)as 1594, ν(COO)s 1342, ∆ν =
252; ν(NO2) 1530, ν(Sn-O-Sn) 624, ν(Sn-C) 519, ν(Sn-O)
468. 1H NMR (ppm) (CDCl3): δ: benzene protons 7.72 (d, 7.8
Hz, 4H); 8.16 (d, 8.24 Hz, 4H); 8.29 (d, 1.8 Hz, 4H); butyl,
CH3 0.86 (t, 7.4 Hz, 12H), 0.91 (t, 7.4 Hz, 12H); CH2 1.28-
1.45 (m, 16H); CH2 1.56-1.78 (m, 32H). 13C NMR (ppm)
(CDCl3): δ: benzene carbons 121.65, 125.82, 130.28, 133.08,
140.16, 148.65; butyl 13.63, 26.74, 26.79, 27.37, 27.56, 28.75,
30.16; COO 170.62. 119Sn NMR (ppm) (CDCl3): δ: -183.76,
-197.49.
RESULTS AND DISCUSSION
In this study, complexes 1-4 have been obtained in solid
state. Complexes 1-4 gave a sharp melting point indicating
the isolation of fairly pure complexes. An outline of the
proposed structure for complexes 1-4 were depicted in Fig. 1.
The micro-elemental analysis for C, H and N data obtained
were in agreement with the predicted formula for complexes
1-4. Based on the micro-elemental analysis, it was believed
that a methanol molecule was present in complex 4 which
acted as a solvate molecule in those similar reported comp-
lexes3,4,6,7. This phenomenon has already been clarified and
the X-ray crystal structure of complex 4 has been reported4.
The ν(O-H) bands of the acid, 2-chloro-4-nitrobenzoic
acid was absent in the infrared spectra of salt and complexes
Preparation of 2-Cl-4-NO2-C6H3COO(C6H5)3Sn.-
CH3OH (4): The title complex was obtained by heating under
reflux a 1:1 molar mixture of triphenyltin(IV) hydroxide
(0.73 g, 2 mmole) and 2-chloro-4-nitrobenzoic acid (0.41 g,
2 mmol) in methanol (50 mL) for 2 h. A clear transparent