Asian Journal of Chemistry; Vol. 25, No.

16 (2013), 9164-9168

http://dx.doi.org/10.14233/ajchem.2013.15086

Synthesis, Characterization and Antibacterial Screening Activity of Dibutyltin(IV) and

Triphenyltin(IV) Complexes Derivatives of 2,4-Dinitrobenzoic and 3,5-Dinitrobenzoic Acids

YIP-FOO WIN1,2,*, SIANG-GUAN TEOH2,* and EMAD YOUSIF3

1
Department of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman, Perak Campus, Jalan Universiti, Bandar Barat, 31900
Kampar, Perak, Malaysia
2
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden Penang, Pulau Pinang, Malaysia
3
Department of Chemistry, College of Science, Al-Nahrain University, Baghdad, Iraq

*Corresponding authors: Fax +605 4661676; Tel: +605 4688888; E-mail: [email protected]

(Received: 4 January 2013; Accepted: 18 September 2013) AJC-14137

In this work, five organotin(IV) carboxylate derivatives of 2,4-dinitrobenzoic and 3,5-dinitrobenzoic acids have been successfully synthesized
and characterized quantitatively and qualitatively. Results of the spectroscopy studies indicated that the coordination took place via
oxygen atoms from the carboxylate anions to the tin atom moieties. From the NMR study, toluene molecule was presented in complexes
3 and 4 which have been clarified and identified. From the preliminary in vitro antibacterial screening study, all the complexes showed
some moderate and selective activity against the tested bacterial strains.

Key Words: 2,4-Dinitrobenzoic acid, 3,5-Dinitrobenzoic acid, Antibacterial activity, Organotin(IV) carboxylate.

INTRODUCTION tometer as KBr disc in the frequency range of 4000-400 cm-1.

The 1H, 1H-13C HMQC and 119Sn NMR were recorded on a
Nowadays, the synthesis, characterization and structural Bruker AC-P 400MHz FTNMR Spectrometer and 13C NMR
study of organotin(IV) complexes have been well-known, was recorded on a Bruker AC-P 300MHz FTNMR Spectro-
established and documented since the first organotin(IV) meter using deuterated CDCl3 and DMSO-d6 as the solvent
compound was successfully isolated in 1850s1-7. The interest and tetramethylsilane (TMS) as the internal standard. Elemen-
and application of organotin(IV) carboxylate complexes have tal C, H and N analyses were carried out on a Fison EA 1108
also received considerable attention as these complexes display CHNS-O analyzer. Tin was determined gravimetrically by
a large array of applications in industries as catalysts, anti- igniting a known quantity of each complex to SnO2. The
fouling agents, wood preservatives, crop protection agents, melting points were determined in an open capillary and were
etc.1. Up-to-date, organotin(IV) carboxylate complexes are uncorrected.
extensively studied due to the structural diversity (monomer, Preliminary in vitro antibacterial screening activity:
dimeric, hexameric and oligomeric) and its biological pro- The synthesized complexes and acids were screened for their
perties1-15. in vitro antibacterial activity against three gram-negative
As part of our interest and research on organotin(IV) (Escherichia coli, Pseudomonas aeruginosa and Klebsiella
work, we have synthesized and characterized organotin(IV) pneumoniae) and two gram-positive (Bacillus subtilis and
carboxylate complexes derivatives of 2,4-dinitrobenzoic acid, Staphylococcus aureus) bacterial strains, by inhibition zone
2,4-(NO 2) 2C6H 3COOH and 3,5-dinitrobenzoic acid, 3,4- method using agar well diffusion method. The seeded agar
(NO2)2C6H3COOH. In addition, the preliminary in vitro anti- (nutrient agar medium) was prepared by cooling the molten
bacterial screening activity of the complexes obtained are agar to 40 ºC and then adding bacterial inoculums containing
carried out and the results are reported herein. approximately 104-106 colony forming units (CFU)/mL. The
bacterial inoculums were spread on the plate containing agar
EXPERIMENTAL
medium and even coverage was ensured before the agar
All the reagents and solvents were purchased commer- solidified. The complexes were dissolved in DMSO to prepare
cially and used without any further purification. Infrared spectra 1.0 mg/mL concentration. By using a sterile metallic borer,
were recorded using a Perkin-Elmer FTIR GX Spectropho- the wells (6 mm in diameter) were dug and the standard drugs
Vol. 25, No. 16 (2013) Synthesis and Antibacterial Activity of Dibutyltin(IV) and Triphenyltin(IV) Complexes 9165

and complexes were introduced into the respective wells. The rences from those of their respective acids. The ν(O-H) bands
plates were incubated immediately at 37 ºC for 20-24 h. The which appeared in the range of 2884-2465 cm-1 for the
activity was determined by measuring the diameter of the respective acids were absent from the infrared spectra of the
inhibition zone (in mm). sodium salts and complexes 1-5. In addition, infrared spectra
Preparation of sodium salts and complexes: The sodium of complexes 1-5 also revealed that the ν(COO)as was shifted
salts of the respective acids were obtained by heating under to a lower wavelength number compared to the parent acids.
reflux a 1:1 molar ratio mixture of sodium hydroxide, NaOH These two distinct appearances indicating the deprotonation
(3 mmol) with the respective acids (3 mmol) in ethanol (50 and coordination of the carboxylate anions to the tin atom
mL) for 2 h. After a few days, white precipitate was obtained. moieties as discussed and reported7.
Complexes 1-5 were synthesized by heating under reflux an The 1H NMR spectral data of complexes 1-5 are summa-
equivalent molar ratio mixture of parent organotin(IV) rized in Table-3, the 1H NMR spectra of complex 3 is depicted
[dibutyltin(IV) oxide or triphenyltin(IV) hydroxide] with the in Fig. 2 as a representative; the 13C and 119Sn NMR spectral
respective acids in appropriate solvents (50-60 mL) for few data of complexes 1-5 are given in Table-4. In general, all the
hours. Then, the respective clear yellow transparent solutions aliphatic groups are located in the upfield regions whereas the
were isolated by filtration and kept in a bottle. After few days, aromatic groups could be found in the downfield regions in
yellow crystals were collected and washed with a small quantity the NMR spectra. Based on the 1H and 13C NMR study, the
of polar solvent. only exceptional case was the occurrence of toluene molecule
in complexes 3 and 4 which have been clarified and identified
RESULTS AND DISCUSSION in our previous report7. From the 119Sn NMR study, the tin
Complexes 1-5 have been obtained in solid state and gave atom in complex 3 was five-coordinated as the chemical shifts
a sharp melting point indicating that the isolation of fairly δ(119Sn) = -127.78 ppm fall in the range between -90 to -190
pure complexes and the micro-elemental analysis for C, H, N ppm which was assigned for five-coordinated tin atom16.
and Sn data obtained were in agreement with the predicted Complexes 1 and 4 were organodistannoxane dimer types and
formula. The micro-elemental and melting point of complexes exhibited two well resolved δ(119Sn) signals as usually expected
1-5 are given in Table-1 and an outline of the proposed reac- (1 = -190.69, -193.80 ppm and complex 4 = -194.27, -203.44
tions and structure for complexes 1-5 are depicted in Fig. 1. ppm)16. From the 119Sn NMR study, all the tin atoms in comp-
For better clarity, all the crystal structure data of complexes lexes 1, 3 and 4 were five-coordinated and exhibited distorted
1-5 (except complex 4) have been reported by our research trigonal bipyramid geometry. The chemical shifts δ(119Sn) of
group9-12. triphenyltin(IV) carboxylate complexes showed a distinct diffe-
The characteristic infrared absorption frequencies (cm-1) rent from the diorganotin(IV) carboxylate complexes17,18.
and assignments for important absorption bands of the acids, Holecek et al.17,18 has proposed that for four-coordinated
sodium salts and complexes 1-5 are listed in Table-2. The triphenyltin(IV) carboxylate complexes, the chemical shifts
infrared spectra of complexes 1-5 revealed the distinct diffe- δ(119Sn) lie between -40 to -120 ppm. In this study, complexes

TABLE-1
MELTING POINT AND MICRO-ELEMENTAL ANALYSIS DATA OF COMPLEXES 1-5
Yield Elemental (%)
Complexes m.p. (ºC)
(%) C H N Sn
[{2,4-(NO2)2C6H3COO(C4H9)2Sn}2O]2 1 87.2 197.8-198.6 40.11 (39.86) 4.86 (4.68) 6.23 (6.20) 26.12 (26.26)
2,4-(NO2)2C6H3COO(C6H5)3Sn 2 82.3 160.4-161.2 53.31 (53.51) 3.00 (3.23) 4.91 (5.00) 21.03 (21.15)
{3,5-(NO2)2C6H3COO}2(C4H9)2Sn.C7H8 3 81.0 197.1-198.6 45.90 (46.61) 4.42 (4.32) 7.48 (7.50) 15.73 (15.88)
[{3,5-(NO2)2C6H3COO(C4H9)2Sn}2O]2.(C7H8)2 4 90.0 210.3-210.9 43.63 (44.61) 4.53 (5.06) 5.61 (5.62) 23.25 (23.83)
3,5-(NO2)2C6H3COO(C6H5)3Sn 5 79.3 174.4-175.2 53.48 (53.51) 2.85 (3.23) 4.95 (5.00) 21.08 (21.15)
Calculated values are given in parenthesis.

TABLE-2
SELECTED INFRARED DATA OF ACIDS, SODIUM SALTS AND COMPLEXES 1-5
Wavelength (cm-1)
Compounds
ν(OH) ν(COO)as ν(COO)s ∆ν ν (Sn-O) ν(Sn-O-Sn)/ν(O-Sn-O)
2,4-(NO2)2C6H3COOH 2882-2535 1723 1346 377 – –
2,4-(NO2)2C6H3COONa – 1569 1342 227 – –
1 – 1659, 1539 1346, 1376 313, 163 475 636
2 – 1599 1345 254 453 –
3,5-(NO2)2C6H3COOH 2884-2465 1701 1348 358 – –
3,5-(NO2)2C6H3COONa – 1624 1346 278 – –
3 – 1629 1345 284 467 684
4 – 1633, 1550 1342, 1400 291, 150 477 632
5 – 1655 1343 312 444 –
2,4-(NO2)2C6H3COONa = sodium salt of 2,4-dinitrobenzoic acid; 3,5-(NO2)2C6H3COONa = sodium salt of 3,5-dinitrobenzoic acid; ∆ν = [ν(COO)as-
ν(COO)s].
9166 Win et al. Asian J. Chem.

NO2
Bu Bu O2 N

O2N C O Sn O C NO2

O O
O Bu
4 Bu 2SnO + 4 HOOC N O2 Bu Sn Sn Bu + 2H 2O
Bu
O
O 2N O O

O 2N C O Sn O C NO2

O2 N
NO 2 Bu Bu
1

Ph O
Ph3SnOH + HOOC NO 2 Ph Sn C NO2 + H2O

O 2N Ph O O 2N

NO2 O2N Bu O NO2

O
toluene Sn
Bu2SnO + 2 HOOC C C + H 2O

NO2 O 2N O Bu O NO 2
H3C
3

CH3 Bu Bu
O 2N NO2

C O Sn O C

NO 2 O 2N O O NO2
toluene O Bu
4 Bu 2SnO + 4 HOOC Bu Sn Sn Bu + 2H2 O
Bu
O
NO 2 O NO2
O2N O
C O Sn O C

O2 N Bu Bu H3C NO2

4
NO2 Ph NO2
O
Ph 3SnOH + HOOC Ph Sn C + H2O

NO2 Ph O NO2
5
Bu = butyl, Ph = phenyl
Fig. 1. Proposed reactions and structure for complexes 1-5

2 and 5 exhibited the δ(119Sn) values at -81.04 and -85.02 ppm, larger than 10 mm but less than 16 mm are considered as
respectively indicating that the tin atoms were four-coordinated moderate and finally larger than 16 mm and above are active19,20.
and have a distorted tetrahedral geometry. Between complexes 1 and 2 which were both derivatives of
The preliminary in vitro antibacterial screening activity 2,4-dinitrobenzoic acid, complex 2 was found to be inactive
of acids and complexes 1-5 are given in Table-5. Inhibition against Klebsiella pneumoniae and Pseudomonas aeruginosa
zones with a diameter less than 10 mm are considered as weak; bacterial strains. However, the antibacterial activity of
Vol. 25, No. 16 (2013) Synthesis and Antibacterial Activity of Dibutyltin(IV) and Triphenyltin(IV) Complexes 9167

TABLE-3
1
H NMR DATA OF ACIDS AND COMPLEXES 1-5
Chemical shift, δ (ppm)
Compounds
Benzene Sn-R (R= Bu and Ph) Toluene
8.09 (d, 8.5 Hz, 1H) H6
2,4-(NO2)2C6H3COOH
8.57 (dd, 2.2 Hz, 8.4 Hz, 1H) H5 – –
(d6-DMSO)
8.76 (d, 2.2 Hz, 1H) H3
0.90 (t, 7.3 Hz, 12H) Hd
7.85 (d, 7.7 Hz, 4H) H6
0.95 (t, 7.4 Hz, 12H) Hd
1 (CDCl3) 8.56 (d, 6.9 Hz, 4H) H5 –
1.32-1.51 *(m, 32H) Hb and Hc
8.75 (s, 4H) H3
1.67-1.85 *(m, 16H) Ha
7.91(d, 8.4 Hz, 1H) H6
7.47-7.50 *(m, 9H) Hm and Hp
2 (CDCl3) 8.36 (dd, 2.2 Hz, 8.4 Hz, 1H) H5 –
7.75-7.78 *(m, 6H) Ho
8.60 (d, 2.1 Hz, 1H) H3
3,5-(NO2)2C6H3COOH (d6- 8.85 (d, 2.3 Hz, 2H) H2 and H6
– –
DMSO) 8.99 (t, 2.2 Hz, 1H) H4
0.97 (t, 7.5 Hz, 6H) Hd CH3; 2.36 (s, 3H)
9.27 (t, 2.2 Hz, 2H) H4
1.50 (sx, 7.3 Hz, 4H) Hc CH2; 7.13-7.17 *(m, 3H)
3 (CDCl3) 9.29 (d, 2.1 Hz, 4H) H2 and H6
1.82 (qn, 7.4 Hz, 4H) Hb CH2; 7.23-7.27 *(m, 2H)
1.99 (t, 8.2 Hz, 4H) Ha
0.83 (t, 7.1 Hz, 12H) Hd CH3; 2.37 (6H, s)
0.96 (t, 6.2 Hz, 12H) Hd CH2; 7.14-7.19 *(m, 6H)
4 (CDCl3) 9.20 (s, 12H) H2, H4 and H6
1.36-1.48 *(m, 16H) Hc CH2; 7.24-7.31 *(m, 4H)
1.81-2.03 *(m, 32H) Ha and Hb
9.16 (t, 2.2 Hz, 1H) H4 7.49-7.55 *(m, 9H) Hm and Hp
5 (CDCl3) –
9.21 (d, 2.1 Hz, 2H) H2 and H6 7.79-7.83 *(m, 6H) Ho
s = singlet, d = doublet, t = triplet, qn = quintet, sx = sextet, dd = doublet of doublet, m = multiplet; o = ortho, m = meta, p = para. Coupling
NO2 m o
6 5 6 5 c b a
1 1 i d
4 4 p Sn CH3-CH2-CH2-CH2-Sn
HOOC NO2 HOOC
3 2 3
constant = Hz, * = overlap. O2N 2 NO2
.

TABLE-4
119
Sn AND 13C NMR DATA OF ACIDS AND COMPLEXES 1-5
Chemical shift (ppm)
Compounds 119 Sn-R (R= Bu and Ph)
Sn Benzene n 119 Toluene COO
J( Sn-13C) (n=1, 2, 3 and 4)
120.25 (C3), 128.66 (C1),
2,4-(NO2)2C6H3COOH
– 132.25 (C5), 133.52 (C6), – – 165.56
(d6-DMSO)
148.75 (C2), 149.56 (C4)
119.47 (C3), 127.21 (C1), 13.56 (Cd), 13.60 (Cd),
-190.69 168.56
1 (CDCl3) 130.59 (C5), 135.62 (C6), 26.73 (Cc), 26.96 (Cc), 27.38 (Cb), –
-193.80 169.67
148.04 (C2), 148.44 (C4) 27.52 (Cb), 28.47 (Ca), 29.63 (Ca)
137.68 (1J = 655.6 Hz) (Ci),
119.58 (C3), 127.26 (C1),
137.27 (2J = 48.9 Hz) (Co),
2 (CDCl3) -81.04 132.21 (C5), 134.58 (C6), – 168.56
129.66 (3J = 65.1 Hz) (Cm),
148.73 (C2), 148.97 (C4)
131.17 (4J = 13.1 Hz) (Cp)
3,5-(NO2)2C6H3COOH 122.82 (C4), 129.66 (C2 and C6),
– – – 164.68
(d6-DMSO) 135.01 (C1), 149.16 (C3 and C5)
21.82
122.92 (C4), 130.55 (C2 and C6), 13.87 (Cd)
3 (CDCl3) -127.78 125.66, 128.59, 171.47
134.78 (C1), 149.09 (C3 and C5) 26.17 (Cc), 26.83 (Cb), 27.10 (Ca)
129.39, 138.23
13.87 (Cd), 13.96 (Cd) 21.76
-194.27 122.20 (C4), 129.96 (C2 and C6),
4 (CDCl3) 27.15 (Cc), 27.79 (Cc), 27.99 (Cb) 125.65, 128.57, 168.82
-203.44 137.22 (C1), 149.13 (C3 and C5)
28.28 (Cb), 29.85 (Ca), 31.11 (Ca) 129.38, 138.21
137.40 (1J = 644.5 Hz) (Ci),
122.27 (C4), 129.68 (C2 and C6), 137.30 (2J = 48.9 Hz) (Co),
5 (CDCl3) -85.02 – 168.10
135.73 (C1), 148.86 (C3 and C5) 130.68 (3J = 64.8 Hz) (Cm),
131.26 (4J = 13.1 Hz) (Cp)
NO2 m o
6 5 6 5 c b a
1 1 i d
4 4 p Sn CH3-CH2-CH2-CH2-Sn
HOOC NO2 HOOC
3 2 3 NO
O2N 2 2
.

triphenyltin(IV) (complex 2) was found to be more active screening bioassays against Bacillus subtilis and Staphylococcus
compared to the dibutyltin(IV) (complex 1) based on the aureus bacterial strains. In addition, in this series of study,
9168 Win et al. Asian J. Chem.

TABLE-5
PRELIMINARY IN VITRO ANTIBACTERIAL SCREENING ACTIVITY OF ACIDS AND COMPLEXES 1-5
Inhibition zone (mm)
Complexes Klebsiella Pseudomonas Staphylococcus
Bacillus subtilis Escherichia coli
pneumoniae aeruginosa aureus.
2,4-(NO2)2C6H3COOH 15 11 12 17 19
1 13 12 10 9 12
2 16 9 - - 19
3,5-(NO2)2C6H3COOH 17 11 10 14 21
3 15 13 11 11 14
4 11 11 10 9 24
5 13 10 8 - 10
*Chloramphenicol 29 - 23 34 30
*Doxycycline 34 24 21 40 28
*Rifampicin 25 24 23 29 37
Agar well diffusion method (in vitro) = 1.0 mg/mL; * = Reference drug.

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