International Journal of Research in Engineering and Innovation Vol-1, Issue-4 (2017), 63-65

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International Journal of Research in Engineering and Innovation

(IJREI)
journal home page: http://www.ijrei.com
ISSN (Online): 2456-6934

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Design of organotin (IV) complexes derived from ciprofloxacin

Duaa Ghazi, Emad Yousif
Department of Chemistry, College of Science, Al-Nahrain University, Baghdad, Iraq
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Abstract
Organotin compounds find a bigger range of technological and industrial applications. Many of these applications involve catalysis,
often in polymer chemistry as stabilizers and in a biological application as well. In this research three organotin (IV) complexes were
synthesized of the type Ph3SnL, Me2SnL2 and Bu2SnL2 of the ligand ciprofloxacin (1-cyclopropyl-6-fluoro-4-oxo-7-piperazin-1-
ylquinoline-3-carboxylic acid). The prepared complexes were characterized by infrared spectral data and elemental analysis. From
the FTIR spectral data octahedral geometry was proposed for Me2SnL2 and Bu2SnL2, while Ph3SnL complex has trigonal bipyramid
geometry. The symmetric and asymmetric stretching vibrations band of carboxylate group showed (∆ν COO -) values were less than
200 cm-1 gave an indication for the ligand to show bidentate characteristic © 2017 ijrei.com. All rights reserved
Keywords: Organotin (IV), Ciprofloxacin, Synthesis, Infrared Spectroscopy
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1. Introduction

The chemistry of organotin (IV) complexes has developed donor atom, such as nitrogen, have revealed new structural
considerably during last 30 years, highlighting the syntheses of types which may lead to complexes with different activity
a number of complexes with interesting characteristics [1–3]. [13].Ciprofloxacin (CFL) is a synthetic, broad-spectrum
Tin can be present as an element in a wide variety of both fluoroquinolone antibacterial agent for oral administration
inorganic and organometallic compounds. Organometallic tin [14]. It is active against a wide variety of aerobic gram-
compounds or organotin are characterized by the presence of negative and gram-positive bacteria. Fluroquinolones are an
at least one covalent carbon - tin bond. Although tin may exist important class of antibacterial compounds which possess a
either in the Sn2+ o r in the Sn4+ oxidation state, almost all fluorine atom at position-6 and a piperazine ring at position-7
organotin have a tetravalent structure. Depending on the of the quinolinone-carboxylic acid (Figure 1). These drugs are
number of organic moieties, the organotin compounds are known to possess an appreciable antibacterial activity [15].
classified as mono-, di-, tri-, and tetraorganotins. In
compounds of industrial importance, methyl, butyl, octyl and
phenyl groups form the organic substituents, while the anion is
usually chloride, fluoride, oxide, hydroxide, carboxylate, or
thiolate [4]. Organotin carboxylates have attracted
considerable attention due to their widely used applications in
many fields such as biological activity and potential
antineoplastic and anti-tuberculosis agents [5], and
cytotoxicity [6] as well as their industrial and agricultural
applications [7–10]. Crystallographic studies have reveal that Figure1. Structure of ciprofloxacin
organotin carboxylates adopt structures which are dependent
on both the nature of the substitute bond to the tin atom and on 2. Methods and Materials
the type of carboxylate ligand [11, 12]. Studies on organotin
(IV) derivatives containing carboxylate ligands with additional Ciprofloxacin, reagent and solvents were supplied from

Corresponding author: Emad Yousif 63

Email Id: [email protected]
 Duaa Ghazi et al/ International journal of research in engineering and innovation (IJREI), vol 1, issue 4 (2017), 63-65

Sigma-Aldrich Chemical Company (Gillingham, UK) and 3.2 Infrared Spectroscopy

used without any further purification. The Fourier Transform
Infrared Spectroscopy (FT-IR) spectra frequencies were By comparing the main FTIR frequencies of the ciprofloxacin
recorded in the range of (400-4000) cm-1 as KBr disc by using and that of tin complexes it shows the that there were two very
FTIR 8300 Shimadzu spectrophotometer. The Elemental strong absorptions peaks in the spectrum of the ligand at
analysis (CHN) of the percentage compositions of the (1708)cm-1 due to the carboxylic group and (1624)cm-1 for
elements (C%, H%, N%) for the prepared compounds were ketone group. The sharp absorption peak at (3529) cm-1 in the
determined using EM-017mth instrument. spectrum of the ligand that stands for (OH) group was not
detected in the spectrum of the complexes, indicating that this
2.1 Synthesis of Triphenyltin (IV) complex moiety participated in the bonding to the metal. The symmetric
and asymmetric modes of the carboxylic group would account
Triphenyltin (IV) complex were synthesized by dissolving the for the bands around (1590-1500) cm-1 [16]. The ∆ν (COO)
free ligand (0.33 g,1 mmol) in hot methanol (15 ml) and adding values were obtained by the following equation [∆ν (COO) =
drop wise a methanolic solution of Ph3SnCl (0.39 g,1 mmol) νasym (COO)-νsym (COO)] and the result showed ∆ν (COO) <
in (10 ml) with stirring. The resulting solution was stirred at 200 cm1, in this case the (COO) considered as bidentate [17].
room temperature for 10 min and then refluxed for 6 h. It was The IR spectral data for the organotin complexes showed new
filtered and the volatiles were removed in vacuum, which on absorption bands. These bands are assigned for ν (Sn-C), ν (Sn-
recrystallization from methanol afforded white powder. O), and ν (Sn-N) that resonate within the 516-540, 447-426,
and 408-416 cm-1 regions respectively. The appearance of such
2.2 Synthesis of Diorganotin (IV) complexes bands give approve for the coordination between ligand and Sn
(IV). The coordination takes place between secondary amine,
The free ligand (2 mmol) dissolved in 20 ml of methanol was carboxylate and alkyl or phenyl group [18, 19]. From the FTIR
slowly added, with constant stirring, to methanolic solution of spectral data an octahedral geometry was proposed for
Me2SnCl2 or Bu2SnCl2 (1 mmol). The mixture was refluxed for Me2SnL2 and Bu2SnL2, while Ph3SnL complex has trigonal
8 h. The resulting solution was filtered and concentrated in bipyramid geometry. The elemental content of the Sn (IV)
vacuum. On the recrystallization from methanol gave an off complexes were observed by elemental analysis. The result
white to pale yellow powder. shows generally an agreement with the calculated values of the
ligand and its complexes.
3. Result and discussion
Table 2. Melting points and Elemental Analyses (%)Calcd (Found)
3.1 Synthesis for L and Sn(IV) complexes.
Melting
Compound Color C% H% N%
point
Four organotin complexes, Ph3SnL, Me2SnL2, Bu2SnL2 and White 61.56 5.48 12.67
Bu2SnOL were synthesized from reactions between L > 300
(61.93) (6.02) (12.59)
diorganotin dichlorides or triorganotin chloride with White 61.7 4.88 6.17
ciprofloxacin as a ligand (L) in methanol under reflux Ph3SnL > 300
(56.58) (5.15) (6.54)
conditions for 6–8 h (figure 2 and 3). a 1:1 molar ratio of L and Pale 53.28 5.22 10.33
Me2SnL2 > 300
Ph3SnCl was used In the case of Ph3SnL, while, a 2:1 molar yellow (53.98) (5.60) (10.51)
ratio of L and R2SnCl2 (R = Me, Bu) was used for the Bu2SnL2
Off
> 300
56.32 6.08 9.38
production of Me2SnL2 and Bu2SnL2. The structures of Sn (IV) white (56.65) (6.70) (10.14)
complexes were characterized by and FTIR spectroscopy and
elemental analysis.

Table 1. FTIR spectroscopic data for L and organotin (IV)

complexes.
Band L Ph3SnL Me2SnL2 Bu2SnL2
Assignment
O-H 3529 — — —
N-H 3433 3406 3448 3444
C=O
carboxyl group 1708 1732 1730 1733
C=O ketone
group 1624 1627 1628 1627 Figure 2: Synthesis of triphenyltin (IV) complex
ν (COO) asym 1575 1589 1590 1587
ν (COO) sym 1509 1508 1507 1510
(COO)ν∆ 66 81 83 77
Sn-C — 540 520 525
Sn-O — 440 447 432
Sn-N — 410 415 408

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 Duaa Ghazi et al/ International journal of research in engineering and innovation (IJREI), vol 1, issue 4 (2017), 63-65

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