Journal of Organometallic Chemistry 723 (2013) 214e223

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Journal of Organometallic Chemistry

journal homepage: www.elsevier.com/locate/jorganchem

Synthesis, characterization, crystal structures and electrochemical studies of

organotin(IV) carboxylates
Muhammad Iqbal a, Saqib Ali a, *, Niaz Muhammad b, Masood Parvez c, Peter Langer d,
Alexander Villinger d
a
Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan
b
Department of Chemistry, Abdul Wali Khan University, Mardan, KPK, Pakistan
c
Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada
d
Department of Organic Chemistry, Institute of Chemistry, University of Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Four new organotin(IV) compounds [Me3SnL] (1), {[Me2SnL]2O}2 (2), Bu2SnL2 (3) and [Bu3SnL] (4), where
Received 24 July 2012 L ¼ O2C(C2H5)CCHC6H4F have been synthesized by refluxing the corresponding organotin(IV) chlorides
Received in revised form with sodium (E)-2-(2-fluorobenzylidene) butanoate (NaL) in dry toluene except 2 for which Me2SnO was
24 September 2012
refluxed with (E)-2-(2-fluorobenzylidene) butanoic acid (LH) in the same solvent. NaL and all the
Accepted 2 October 2012
compounds were characterized by FT-IR, 1H NMR and 13C NMR spectroscopy. NaL and compounds 1 and
2 were also characterized by X-ray single crystal analysis which confirmed a linear polymeric structure
Keywords:
for compound 1 and a stannoxane for 2. The structural analyses have shown a bridging behavior of the
Organotin(IV) carboxylates
Sodium (E)-2-(2-fluorobenzylidene)
ligand in trimethyl- and tributyl-, chelating as well as bridging behavior in dimethyl- and a chelating
butanoate bidentate mode of coordination in dibutyltin(IV) compound which is also confirmed from the crystal
Crystal structures analysis for compounds 1 and 2. Cyclic voltammetry was used to evaluate the electrochemical, kinetic
Stannoxane and thermodynamic parameters for the electron transfer processes of compounds 1e4. Predominantly
Cyclic voltammetry adsorption controlled redox processes were exhibited by the slope of log ip vs. log v plots. The values of
the diffusion coefficient (Do) indicated the role of solvent in the mobility of the electro-active species to
some extent but the overall rate of the redox process was typical of the adsorption controlled process and
could not be explained on the basis of solvation effects. The values of formal potential and charge transfer
coefficient were also calculated.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction ladder shaped, hexameric [8] and polymeric (linear [9], zigzag [10]
and stannoxanes such as 1D, 2D, and 3D [8]) structures. Apart from
Owing to the ability of tin to form stable complexes with carbon these, some cyclic species have also been reported [8]. The mono-
and hetero atoms, organotin derivatives are becoming the focal alkyltin(IV) tricarboxylates exhibit relatively less structural diver-
point of many research areas such as organic synthesis, synthesis of sity and are not as widespread as the di- and triorganotin(IV)
polyesters, polyurethanes and in the crosslinking of silicon and carboxylates [11].
catalysis such as esterification and trans-esterification reactions [1]. Although a number of new synthetic techniques such as sol-
Organotin(IV) carboxylates constitute a class of organoitn(IV) vothermal synthesis and other are commonly employed for the
compounds and are extensively being studied nowadays due to synthesis of organotin(IV) carboxylates, the conventional synthetic
their potential biocidal activity, cytotoxicity, industrial and agri- techniques such as standard schlenk technique [8,12] and reflux
cultural applications. Organotin(IV) compounds containing methods are still in common use [10]. In this research work the
carboxylate ligand with additional donor atoms such as N, O or S complexes are synthesized using the reflux method. The ligand is
have been shown to exhibit new structural geometries and hence used to react with the organotin(IV) chlorides under reflux condi-
new potential activities [1,2,7]. The most common geometries are tions. The synthesized organotin(IV) compounds consist of linear
monomeric (tetrahedral, octahedral [3], skew trapezoidal [4], polymeric carboxyl bridged [Me3SnL]n (1) and [Bu3SnL]n (4), tetra-
trigonal bipyramidal [5,6]), dimeric, tetrameric [7], oligomeric, meric tetraorganodistannoxane {[Me2Sn(OOC(C2H5)CCHC6H4F)]2O}2
(2) and monomeric skew trapezoidal Bu2SnL2 (3); each self assembled
* Corresponding author. Tel.: þ92 51 90642130; fax: þ92 51 90642241. from the respective organotin(IV) derivative and the ligand under
E-mail address: drsa54@yahoo.com (S. Ali). reflux conditions.

0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.10.006
 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223 215

Regarding the biological activities of metal complexes, the Table 1

oxidation state and redox behavior of the central metal atom are of Crystal data and structure refinement parameters for NaL and compounds 1 and 2.

prime importance among several other parameters [13]. The labili- Compound NaL 1 2
zation of the attached ligands, resulting in the biologically active Moiety Formula C11 H18 F Na O5.50 C14 H19 F O2 Sn C26 H32 F2 O5 Sn2
species as well as the inherent activity of the complex without ligand Formula mass 280.24 356.98 699.90
dissociation is critically affected by the former of the two mentioned (g mol1)
Crystal system Orthorhombic Orthorhombic Monoclinic
properties. Hence the in vivo interconversion of different oxidation
Space group Fdd2 P 21 21 21 P 21/n
states of the metal complexes has been reported to alter their
properties drastically [14,15]. The redox potential of an organome- Unit cell dimensions
a (
A) 12.4218(8) 6.6797(3) 10.5396(3)
tallic compound is a function of several factors. Besides synthesis, the b (
A) 75.112(5) 10.1047(4) 15.5407(4)
role of the electronic properties of the attached ligands, geometry of c (
A) 5.6337(3) 21.7370(11) 17.3810(4)
the complex and the nature of organic moiety attached to metal in a ( ) 90.00 90.00 90.00
determining the redox potential of the synthesized organotin(IV) b ( ) 90.00 90.00 106.7558(15)
g ( ) 90.00 90.00 90.00
carboxylates has been studied and discussed in the present work.  3
V (A ) 5256.4(6) 1467.17(12) 2726.01(12)

2. Experimental q Ranges
for data
Collection ( ) 2.17  25.00 3.58  30.02 2.45  26.04
2.1. Materials and methods Z 16 4 4
rcalc.(g cm3) 1.417 1.616 1.705
Dimethyltin(IV) oxide, trimethyl-, tributyl- and dibutyltin(IV) F(000) 2368 712 1384
Crystal 0.09  0.08 0.16  0.12 0.16  0.14
chlorides were purchased from Aldrich and used without further
size (mm)  0.02  0.12  0.04
purification. All the solvents were dried according to the reported T (K) 123(2) 123(2) 173(2)
standard procedures [16]. The melting points were obtained in
Index ranges
a capillary tube using a Gallenkamp, serial number C040281, UK,
h 14e14 9e9 13e13
electro-thermal melting point apparatus. FT-IR spectra were k 88e87 14e14 19e18
recorded on a Nicolet-6700 FT-IR spectrophotometer, thermo- l 6e6 30e30 21e21
scientific, USA, in the range from 4000 to 400 cm1. 1H and 13C NMR Total data 1268 2447 5272
spectra were recorded on Bruker Advance Digital 300 MHz NMR Unique data 1169 2419 4807
Final R indices R1 ¼ 0.0416 R1 ¼ 0.0305 R1 ¼ 0.0302
spectrometer, Switzerland, using CDCl3 as an internal reference [I>/2s(I)] wR2 ¼ 0.0781 wR2 ¼ 0.0918 wR2 ¼ 0.0761
[d1H (CDCl3) ¼ 7.25 and d13C (CDCl3) ¼ 77.0 ppm]. The spectra were
acquired at room temperature (298 K).

2.2. X-ray crystallographic studies

containing 0.1 M tertiarybutylammonium perchlorate (TBAP)
under a N2 saturated environment in a conventional three-
A colorless prismatic crystal of 1 and colorless plate crystals of 2
electrode cell with saturated calomel electrode as reference,
and NaL were used for data collection. The crystals were coated with
a Platinum wire having diameter of 0.6 mm as counter and a bare
Paratone 8277 oil (Exxon) and mounted on a glass fiber. All
glassy carbon electrode (GCE) with a surface area of 0.196 cm2 as
measurements were made on a Nonius Kappa CCD diffractometer
the working electrode. Prior to experiment the GCE was polished
with graphite monochromated Mo-Ka radiation. Details of crystal
with alumina (Al2O3) on a nylon buffing pad followed by washing
data and structure refinement have been provided in Table 1. The
with acetone and finally with distilled water. Electrochemical
data were collected at a temperature of 173(2) K for 1 and 123(2) K for
measurements were carried out at room temperature (25  0.5  C).
2 and NaL using u and 4 scans, corrected for Lorentz and polarization
effects and for absorption using multi-scan method [17,18].
The structures were solved by the direct methods [19] and 2.4. Synthesis
expanded using Fourier techniques [20]. The non-hydrogen atoms
were refined anisotropically. Hydrogen atoms were included at Reactions of the sodium salt of the ligand (NaL) with trimethyl,
geometrically idealized positions and were not refined. The final dibutyl and tributyltin(IV) chlorides in 1:1, 2:1 and 1:1 molar ratios,
cycle of full-matrix least-squares refinement using SHELXL97 [21a] respectively afforded air stable compounds 1, 3 and 4 whereas, to
converged with unweighted and weighted agreement factors, R affect the synthesis of 2, the ligand (LH) was refluxed with dime-
and wR ¼ 0.0305 and 0.0918 (all data) for 1, 0.0302 and 0.0761 (all thyltin(IV) oxide in 2:1 molar ratio. The general synthetic proce-
data) for 2 and 0.0416 and 0.0781 for NaL, and goodness of fit, dures and numbering pattern are shown in Scheme 1.
S ¼ 1.076, 1.053 and 1.154, respectively. The absolute structure
parameter x [21b] indicated the presence of racemic twinning in NaL. R3 SnCl þ NaL/R3 SnL þ NaCl
(1)
A TWIN instruction with the default matrix R ¼ (10 0, 0 10, 0 0 1) R ¼ Methylð1Þ; n  Butylð4Þ
in the least-squares refinement cycles lead to a BASF parameter of
0.2147. The Friedel pairs of reflections (865) were merged. 4ðmethylÞ2 SnO þ 4LH/ðmethylÞ8 Sn4 L4 O2 ð2Þ þ 2H2 O (2)
The weighting schemes were based on counting statistics and
the final difference Fourier maps were essentially featureless. The ðn  ButylÞ2 SnCl2 þ 2NaL/ðn  ButylÞ2 SnL2 ð3Þ þ 2NaCl (3)
figures were plotted with the aid of ORTEP-3 [22].

2.3. Electrochemistry 2.4.1. Synthesis of sodium (E)-2-(2-fluorobenzylidene) butanoate (NaL)

The ligand viz., (E)-2-(2-Fluorobenzylidene) butanoic acid (LH)
Voltammetric experiments were performed using an SP-300 has been synthesized and reported earlier [23]. The sodium salt of
potentiostate, serial number 0134, BioLogic Scientific Instruments, the ligand was prepared by drop wise addition of an equimolar
France. Measurements were carried out in DMSO solution amount of sodium hydrogen carbonate dissolved in distilled water
216 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223

10 11
H2C CH3
8 9
4 3 2 1
7 C C C OH
H
6 F
5 O
Ligand (LH)

α γ
δ
Sn CH3
β

α
Sn CH3

Scheme 1. General synthetic procedure and numbering pattern of LH and compounds 1e4.

to an ethanolic solution of ligand. The solution was stirred for 1 h at (0.864 g, 4 mmol). (Yield: 1.15 g, 80%). FT-IR (cm1): 1610
60  C followed by filtration. The filtrate was allowed to evaporate to y(OCO)asym, 1483 y(OCO)sym, Dy ¼ 127, 523 y(SneC), 456 y(SneO). 1H
get the colorless crystals of the salt. M.p. 88e89  C. IR (cm1): 1643 NMR (CDCl3, ppm): 7.75 (s, 1H, H3), 7.34e7.09 (m, ArH, 4H), 2.52
y(OCO)asym, 1388 y(OCO)sym, Dy ¼ 255. 1H NMR (CDCl3, ppm): 7.2 (s, (q, H10, 2H), 1.20 (t, H11, 3H), 1.78-1.77 (m, Ha, and Hb, 8H), 1.49e
1H, H3), 7.25e6.92 (m, 4H, Ar-H), 2.22 (q, H10, 2H), 0.86 (t, H11, 3H). 1.42 (m, Hg, 4H), 0.95 (t, Hd, 6H). 13C NMR (CDCl3, ppm): 177.5
13
C NMR (CDCl3, ppm): 177.7 (C-1), 130.4 (C-2), 144.5 (C-3), 124.24 (C-1), 130.1 (C-2), 136.9 (C-3), 124.0{14.2} (C-4), 162.4{248.2} (C-5),
{15.0} (C-4), 159.8{243.8} (C-5), 115.2{21.8} (C-6), 129.4{8.2} (C-7), 115.7{21.8} (C-6), 132.4{8.1} (C-7), 131.0{3.8} (C-8), 130.1{3.0} (C-9),
128.2{3.0} (C-8), 123.91{3.0} (C-9), 21.4 (C-10), 12.5 (C-11). 21.5 (C-10), 13.8 (C-11), 25.4 [C-a, 1J (119Sn13C) ¼ 790 Hz], 26.8
[C-b, 2J (119Sn13C) ¼ 38 Hz], 26.4 [C-g, 3J (119Sn13C) ¼ 82 Hz], 13.6
2.4.2. Trimethylstannyl 2-(2-fluorobenzylidene) butanoate (1) (C-d).
The sodium salt of the ligand (NaL) (0.500 g, 2.33 mmol) was
refluxed for 6 h with trimethyltin(IV) chloride (0.465 g, 2.33 mmol) in 2.4.5. Tributylstannyl 2-(2-fluorobenzylidene)butanoate (4)
dry toluene in a two necked round bottom flask. At the end the turbid Compound 4 was prepared and crystallized in the same way as 1
solution was allowed to cool down to room temperature. The sodium using tributylstannyl chloride (0.651 g, 2 mmol) and NaL (0.432 g,
chloride formed was filtered off and the filtrate was rotary evaporated. 2 mmol). (Yield: 0.70 g, 75%). FT-IR (cm1): 1649 y(OCO)asym, 1454
The resultant solid was recrystallized from ethanolic solution. (Yield: y(OCO)sym, Dy ¼ 195, 523 y(SneC), 455 y(SneO). 1H NMR (CDCl3,
0.80 g, 83%). M.p. 104e105  C. FT-IR (cm1): 1641 y(OCO)asym, 1453 ppm): 7.65 (s, 1H, H3), 7.65e7.06 (m, ArH, 4H), 2.48 (q, H10, 2H),
y(OCO)sym, Dy ¼ 188, 543 y(SneC), 541 y(SneO). 1H NMR (CDCl3, ppm): 1.15 (t, H11, 3H), 1.70-1.62 (m, Ha and Hb, 12H), 1.44e1.28 (m, Hg,
7.7 (s, 1H, H3), 7.19e7.06 (m, Ar-H, 4H), 2.47 (q, H10, 2H), 1.15 (t, H11, 6H), 0.94 (t, Hd, 9H). 13C NMR (CDCl3, ppm): 172.8 (C-1), 130.1 (C-2),
3H), 0.63 [Ha, 9H, 2J (119/117Sn1H) 58/56 Hz]. 13C NMR (CDCl3, ppm): 138.9 (C-3), 124.7{14.3} (C-4), 160.3{247.5} (C-5), 115.5{21.8} (C-6),
177.7 (C-1), 130.4 (C-2), 144.5 (C-3), 124.2{14.2} (C-4), 159.8{247.5} (C- 129.6{8.2} (C-7), 130.0{3.8} (C-8), 123.8{3.8} (C-9), 21.6 (C-10), 13.8
5), 115.2{21.8} (C-6), 129.4{8.3} (C-7), 128.2{3.8} (C-8), 123.9{3} (C-9), (C-11), 16.6 [C-a, 1J (119/117Sn13C) ¼ 358/343 Hz], 27.9 [C-b, 2J
21.4 (C-10), 12.5 (C-11), 2.2 [C-a, 1J (119Sn13C) ¼ 397 Hz]. (119Sn13C) ¼ 21 Hz], 27.0 [C-g, 3J (119Sn13C) ¼ 64 Hz], 13.7 (C-d).

2.4.3. Bis(-2-(2-fluorobenzylidene)butanoato)tetra- 3. Results and discussion

methyldistannoxane (2)
Compound 2 was prepared by fluxing dimethylstannyl oxide 3.1. Spectroscopic studies
(0.659 g, 4 mmol) with LH (0.776 g, 4 mmol) in dry toluene for 6 h
using Dean-stark apparatus. The reaction mixture was then cooled, 3.1.1. FTIR spectra
filtered and subsequently rotary evaporated to get the dry product The frequencies of interest are those associated with COO, SneC
which was then recrystallized in the same way as 1. (Yield: 0.95 g, and SneO groups. The absorption band appearing in range 455e
70%). M.p. 122e123  C. FT-IR (cm1): 1540 y(OCO)asym, 1398 476 and 523e551 cm1 in the respective FT-IR spectra of the
y(OCO)sym, Dy ¼ 142, 551 y(SneC), 476 y(SneO). 1H NMR (CDCl3, compounds 1e4, that were absent from the spectrum of the free
ppm): 7.8 (s, 1H, H3), 7.35 - 7.09 (m, Ar-H, 4H), 2.51 (q, H10, 2H), 1.19 ligand (NaL), were assigned to the SneO [1,6,24,25] and SneC
(t, H11, 3H), 0.93 and 0.99 [Ha, 6H, 2J (119/117Sn1H) 75/71 Hz]. 13C stretching modes of vibration, respectively. The asymmetric and
NMR (CDCl3, ppm): 177.5 (C-1), 130.2 (C-2), 136.5 (C-3), 123.7{14.3} symmetric vibrations due to COO moiety were observed at 1649e
(C-4), 160.4{248.2} (C-5), 115.7{21.8} (C-6), 130.3{8.2} (C-7), 130.02 1610 and 1375e1483 cm1, respectively. The difference between
{3.7} (C-8), 128.6{3.0} (C-9), 21.5 (C-10), 13.8 (C-11), 4.8 (C-a). these two modes of vibration (Dy) indicates the mode of coordi-
nation of the ligand to the tin centre [26]. The reduction in Dy
2.4.4. Dibutylstannyl bis(-2-(2-fluorobenzylidene)butanoate (3) values of COO moiety of the ligand is attributed to the reduction of
Compound 3 was prepared and crystallized in the same way as 1 electron density on its oxygen atoms consequent upon coordina-
employing dibutylstannyl chloride (0.608 g, 2 mmol) and NaL tion to tin(IV) moiety. In the present work, 1, 2 and 4 showed
 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223 217

Table 2 density transfer from the ligand to the acceptor tin atom. The
Selected bond lengths (
A) and bond angles ( ) of NaL. positions of carbon atoms in fluorophenyl group are easily assigned
Bond lengths (
A) Bond angles ( ) with the help of nJ(19F13C) coupling, where n ¼ 1,2,3,4. The
n 19
O1eC1 1.282(4) C1eO1eH10 109.5 J( F13C) coupling constants calculated, are comparable to those
O1eH10 0.8400 O2eC1eO1 123.2(4) reported in the literature. The reported ranges of the nJ(19F13C)
O2eC1 1.246(5) O2eC1eC2 118.8(3) coupling, where n ¼ 1,2,3 and 4 are 230e265, 15e25, 7e12 and 3 Hz,
C1eC2 1.515(5) O1eC1eC2 118.0(4)
respectively [28e30]. The values observed for nJ(19F13C) coupling
Na1eO3W 2.379(3) O3WeNa1eO4W 90.37(11)
Na1eO4W 2.388(3) O4WeNa1eO5W 108.26(12) are 244e248, 1521, 8 and 34 Hz for n ¼ 1,2,3 and 4, respectively.
Na1eO5W 2.401(3) O5WeNa1eO6W 76.13(10) The satellites due to nJ [119/117Sn13C] coupling, shown by the
Na1eO6W 2.469(4) O3WeNa1eO6W 85.65(10) compounds 1, 3 and 4, have been calculated which are important
indicators for the structural elucidation of organotin(IV) carboxyl-
ates. Among the synthesized compounds, 1 exhibited 1J [119Sn13C]
a bridging structure while 3 showed a chelating mode of coordi- being of the order of 397 Hz, confirming a monomeric tetrahedral
nation for the ligand. These observations were further supported by geometry in solution [31]. In case of compounds 3 and 4, nJ
the crystal structures of the compounds. The stannoxane structure [119Sn13C] values are 790, 38, 82 and 358, 21, 64 Hz respectively.
for 2 was supported from its characteristic absorption band of These values suggest a skew trapezoidal geometry around tin for 3
medium intensity observed at 693 cm1 assignable to SneOeSn and a monomeric tetrahedral geometry for 4 in solution form. This
functionality [24,27]. shows that a reduction of coordination number of tin atom in
solution occurs in triorganotin(IV) carboxylates (1 and 4). On the
3.1.2. 1H NMR spectra other hand, the diorganotin(IV) compounds (2 and 3) retain their
The methyl protons attached to the tin atom in compounds 1 geometries in solution as well.
and 2 exhibited a well defined singlet with 2J (119/117Sn1H) values
58/56 and 75/71 Hz, respectively. The terminal methyl protons of 3.2. Crystal structure
butyl groups attached to tin atom in compounds 3 and 4 gave
a clear triplet each while the rest of the protons exhibited a multi- 3.2.1. Structure of NaL
faced pattern. The sharp singlet observed for the single proton The structure refinement parameters and selected bond lengths
attached to C-3 was shifted from 7.8 ppm, to 7.6e7.7 ppm, observed and bond angles of the sodium salt of the ligand (NaL) are given in
for free ligand and compounds 1e4, respectively. The methyl and Tables 1 and 2 while its ORTEP is shown in Fig. 1 which reveals that
methylene protons of the coordinated ligand gave rise to triplet and each of the sodium ions is coordinated by six water molecules.
quartet at 0.86 and 2.22 ppm, respectively in the spectra of all the Oxygen atom of each water molecule acts as a bridge between the
compounds. 2J [119/117Sn1H] in Hz are also calculated and helped two sodium ions. This constitutes an infinite 2D sheet of the hex-
to confirm four coordinated geometry around tin atom in acoordinated sodium ions where the hydrogen atoms of the water
compound 1 and the retention of six coordinated geometry around molecules are oriented outside. These hydrogen atoms are
tin centre in 2, in solution form. responsible for hydrogen bonding with the oxygen atoms of the
carboxylate moiety of the ligand molecules resulting in their
3.1.3. 13C NMR spectra attachment to the ionic layer in a perpendicular manner. Addi-
The 13C NMR spectra of all the complexes showed a more or less tionally, every sodium ion is in a position suitable enough to
downfield shift of all the carbon resonances compared with those of establish weaker interaction with a lone pair of an oxygen atom of
the free ligand (NaL). The shift is a consequence of the electron each the two ligand molecules lying on its two opposite sides.

Fig. 1. ORTEP diagram of the sodium salt of the ligand (NaL).

218 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223

Fig. 2. Packing of NaL showing double layers of ligand molecules sandwitched between those of hydrated sodium ions in aoc plane.

Looking at the packing diagram of the ligand, shown in Fig. 2, it is The compound exhibits a carboxylate bridged motif in which the
seen that both sides of the ionic layer are occupied by ligand Sn center shows trigonal-bipyramidal coordination, the equatorial
molecules constituting a double layer of the latter, sandwiched plane being defined by the three methyl groups while the axial
between two consecutive layers of the former. positions are occupied by two oxygen atoms. According to the
As is evident from the structure, the ligand molecule is lying as literature [32], the geometry around Sn atom can be characterized by
such in the crystal lattice and there is no direct OeNaþ bond, the value of s ¼ (bea)/60, where b is the largest of the basal angles
however, there are some noteworthy variations in the properties of around the Sn atom. The angle values a ¼ b ¼ 180 correspond to
the NaL compared to those of HL reported earlier by our research a square-pyramidal geometry, and the value of a ¼ 120 corresponds
group [23]. In this regard, apart from the change in physical prop- to a perfect trigonal-bipyramidal geometry. Thus the s value is equal
erties, there is a considerable shortening of the acidic OeH bond to zero for a perfect square-pyramidal and unity for perfect trigonal-
length in NaL compared to that in HL. The O1eH10 bond length in bipyramidal geometry. The calculated s value for 1 is 0.82 which
NaL is 0.84 (
A) as opposed to 0.97(2) (
A) in HL. This may be attributed indicates distorted trigonal-bipyramidal geometry around Sn atom.
to the reduction of electron density on O1 as a consequence of its The angle OeSneO is 171.17 while the sum of the equatorial CeSne
weak interaction with sodium ions resulting in strengthening and C angles is 358.9 . The overall structure is an infinite zigzag chain of
shortening of OeH bond in crystal lattice. This observation is in line carboxylate bridged trimethyltin(IV) species (Fig. 4).
with the shortening of C1eO1 bond (1.282(4) ( A)) of NaL compared
to that of HL (1.3006(18) (
A)), again attributable to the same reason. 3.2.3. Crystal structure of compound 2
The molecular structure of compound 2 is shown in Fig. 5
3.2.2. Crystal structure of compound 1 whereas the crystal data, selected bond lengths and bond angles
The molecular structure of compound 1 is shown in Fig. 3 are listed in Tables 1 and 4.
whereas the crystal data, selected bond lengths and bond angles The geometries of all the tin atoms in 2 can be classified into two
are listed in Tables 1 and 3. types: pentacoordinated tin (Sn2), and hexa-coordinated tin (Sn1).
The pentacoordinated tin atoms (Sn2) form three short SneO bonds
with three oxygen atoms: two from the Sn2O2 moiety and the other
one from the carboxylate group, together with the two bonds to
methyltin groups. The Sn2 atom may be viewed as highly distorted
trigonal bipyramid with the axial site occupied by the O(5) and
O(3) atoms (:(O5)eSn(2)eO(3) ¼ 166.69(9) ) having s ¼ 0.418.
The five-coordinate geometry about each of the Sn2 is due to the
monodentate coordination mode of the carboxylate ligand. Each of
the hexacoordinated tin atoms, Sn1, forms four short SneO bonds
with four oxygen atoms: one from the Sn2O2 moiety and the other
three from two different carboxylate groups. Together with the two
bonds to methyltin groups, the Sn1 atom may be viewed as distorted

Table 3
Selected bond lengths (
A) and bond angles ( ) of compound 1.

Bond lengths (
A)
Sn1eC1 2.123(4) O1eC4 1.251(5)
Sn1eC2 2.129(4) O2eC4 1.285(5)
Sn1eC3 2.131(5) O2eSn1 2.173(3)
Sn1eO2 2.173(3) C4eC5 1.508(5)
Sn1eO1 2.394(3)

Bond angles ( )
C1eSn1eC2 116.5(2) C3eSn1eO2 97.56(17)
C1eSn1eC3 121.2(2) C1eSn1eO1 84.09(14)
C2eSn1eC3 121.70(19) C2eSn1eO1 92.75(14)
C1eSn1eO2 87.22(15) C3eSn1eO1 85.65(16)
C2eSn1eO2 92.53(15) O2eSn1eO1 171.17(11)
Fig. 3. ORTEP diagram of compound 1.
 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223 219

Fig. 4. Linear polymeric structure of compound 1.

octahedral in geometry. The largest angle around tin atom is 170.44 irreversible nature of the redox processes is attributed to the
(¼:(O(1)eSn(1)eO(4)). In contrast to the common polymeric instability of the resulting species in DMSO [33].
stannoxanes, this compound is monomeric tetra-nuclear tetraor- The ligand centered relatively weak anodic peaks of the
ganodistannoxane. Here two of the carboxylate ligands exhibit compounds 1e3 occur in the range 0.98e1.13 V. No peak was
a bridging bidentate mode of coordination while the other two observed in the oxidation region of the cyclic voltamogram of
ligands show monodentate mode of coordination (Fig. 6). compound 4 showing its electrochemical stability under the given
conditions. The anomalous behavior of butyl derivatives of orga-
3.3. Electrochemical studies notin compounds has been observed by other researchers too [34].
The reduction signals of all the compounds were observed in
Cyclic voltammetry was used to explore the electrochemical between 0.95 and 1.06 V as shown in Fig. 7. The cathodic signal
redox behavior of compounds 14 and the resulting voltammo- of the compounds is attributed to the reduction of tin(IV) to tin(II)
grams at 100 mV s1 are given in Fig. 7. species [35,36]. Owing to the similarity of the chemical environ-
As is evident from the respective voltammograms, one oxidation ment around central metal in these compounds, the individual
and one reduction peak was observed for each of the four reduction potential values are lying closer to each other. The more
compounds. The large potential difference between the oxidation electron donating butyl groups in 3 and 4, compared to 1 and 2,
and reduction peaks (w2000 mV) provides ample evidence for the render the former pair of compounds less prone to reduction, thus
independent nature of the irreversible redox processes. The slightly shifting their cathodic potential to more negative values.

Fig. 5. ORTEP diagram of compound 2.

220 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223

Table 4 0.03 1
Selected bond lengths (
A) and bond angles ( ) of compound 2.
2
Bond lengths (
A)
0.02 3
Sn1eO5 2.023(2) Sn2eO5 2.032(2) 4
Sn1eC2 2.103(4) Sn2eC14 2.112(4)
Sn1eC1 2.120(4) Sn2eC15 2.113(4)
0.01
Sn1eO1 2.163(2) Sn2eO5 2.174(2)
Sn1eO4 2.265(2) Sn2eO3 2.262(2)

I / mA
Bond angles ( ) 0.00
O5eSn1eC2 107.26(13) O5eSn2eC14 105.82(13)
O5eSn1eC1 111.36(13) O5eSn2eC15 112.14(13)
C2eSn1eC1 140.37(16) C14eSn2eC15 141.61(15) -0.01
O5eSn1eO1 80.88(9) O5eSn2eO5 75.96(9)
C2eSn1eO1 99.98(14) C14eSn2eO5 98.20(12)
C1eSn1eO1 94.57(13) C15eSn2eO5 96.30(12) -0.02
O5eSn1eO4 91.12(9) O5eSn2eO3 91.35(9)
C2eSn1eO4 87.34(14) C14eSn2eO3 89.00(12)
C1eSn1eO4 83.43(13) C15eSn2eO3 84.67(12) -0.03
O1eSn1eO4 170.44(9) O5eSn2eO3 166.69(9)
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
E/V
The combined plots obtained at different scan rates for each of the Fig. 7. Cyclic voltammograms of 1.40 mM compounds 14 at 100 mV s1.
compounds are shown in Fig. 8 that clearly indicate that on
increasing scan rate, the cathodic peak potential is displaced to
This shows that solvation does play a role in determining the rate of
more negative potential suggesting irreversibility of the reduction
mass transport of these compounds to the electrode surface.
process of the compounds.
However, being adsorption controlled the values of Do and their
For irreversible processes the peak current is given by the
mutual order is not typical of a diffusion controlled process.
RandleseSevcik model (Eq. (4)) [37]:
Fig. 9(b) shows the linear relation between log ipc vs. log v with

 slope values of 0.19, 0.22, 0.12 and 0.17 for compounds 14,
2:99  105 nðanÞ1=2 AC * Do v1=2
1=2
ip ¼ (4) respectively. It reveals predominantly adsorption controlled redox
processes [38]. The general linear regression equation for this
where ip is the peak current in amperes, a is the charge transfer relation is given as follows:
coefficient, n is the number of electrons involved in the redox
process, Do is diffusion coefficient in cm2 s1, C* is the bulk h i
concentration of the compound in mol cm3, A is the surface area of log ipc ½mA ¼ þslope log v Vs1 þ intercept
the working electrode in cm2 and v is the potential scan rate in
V s1. The values of the diffusion coefficient for the redox processes For getting further insight into the nature of the electrochemical
are calculated employing Eq. (4) by putting various cathodic redox process, the charge transfer coefficients (a) of the
parameters in it using the slope of ipc (mA) vs. v1/2 (Vs1) plot compounds 1e4 were determined by the application of Bard and
(shown in Fig. 9(a)). The values of Do thus calculated for compounds Faulkner relation [39]. According to them the value of a can be
14 are listed in Table 4, which show that the mobility of lower calculated as
coordinated Sn4þ species is hampered by the facile attachment of  
relatively more solvent molecules. The slow diffusion of 4 is an ¼ 47:7= Epa  Epa =2 mV (5)
attributed to its tetracoordinated geometry around tin(IV) center
leading to high solvation by solvent molecules and the presence of where Epa/2 is the potential where the current is at half the peak
relatively longer butyl groups. Looking at the coordination number value.
and steric effects of the attached groups to the tin centre, the ease of The values of charge transfer coefficient (a) for the compounds
solvation of the molecules would vary in the order: 1 > 4 > 2 > 3. were calculated using Eq. (5) and are listed in Table 5.

Fig. 6. Packing diagram of compound 2.

 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223 221

A 0.04 B 0.05
160 mVs-1
0.04
0.03 160 mVs-1
0.03
40 mVs-1
0.02
0.02 40 mVs-1

I / mA
I / mA

0.01 0.01
0.00 0.00

-0.01 -0.01
-0.02
-0.02
-0.03
-0.03
-0.04
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
E/V E/V
C 0.04 D 0.10

160 mVs-1
0.03 160 mVs-1 0.08

0.02 0.06
40 mVs-1
40 mVs-1
I / mA

0.01

I / mA
0.04
0.00
0.02
-0.01
0.00
-0.02
-0.02
-0.03
-0.04
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
E/V E/V

Fig. 8. Cyclic voltammogramms of compounds 1(A), 2 (B), 3(C) and 4(D) each at scan rates of 40, 60, 80, 100, 120, 140 and 160 mV s1.

For irreversible electrode processes the value of E is given by

Eq. (6) [40e42]: Table 5
CV parameters for the reduction of the compounds.

E ¼ Eo þ 2:303 RTko =anF  2:303 RT=anF log v (6) Compound E (V) an D  107 k (s1)
(cm2 s1)
where Eo is the formal redox potential, ko is the standard hetero- 1 0.89 0.25 4.80 1.36
geneous rate constant and F is the Faraday constant. The values of 2 0.92 0.28 4.02 0.70
heterogeneous rate constant (ko) were determined from the inter- 3 0.96 0.27 4.27 1.66
4 0.99 0.30 3.13 2.11
cept of potential vs. negative logarithm of scan rate plot (shown in
Fig. 10(a)) by putting various parameters in Eq. (6). The values of

a 1 b 4.86 4
2
19 3 2
4.83
18 1
4 4.80
17 3
log Ipc
-Ipc / uA

4.77
16

15 4.74

14 4.71

0.20 0.25 0.30 0.35 0.40 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
1/2
v -log v

Fig. 9. Plots of cathodic peak current vs. square root of the scan rate (a) and log of cathodic peak current vs. log scan rate (b) for compounds 14.
222 M. Iqbal et al. / Journal of Organometallic Chemistry 723 (2013) 214e223

a b 1.06 4
1.06
2
1.04 1.04 3

1.02 1.02
4
1.00 1.00 1

-Epc / V
-Epc / V

0.98 0.98
3
0.96 0.96
2
0.94 0.94

0.92 0.92
1
0.04 0.06 0.08 0.10 0.12 0.14 0.16
0.72 0.84 0.96 1.08 1.20 1.32 1.44
-1
-log v v / Vs

Fig. 10. Plots of cathodic peak potential vs. log of scan rate (a) and scan rate (b) for compounds 1e4.

formal potential (E) were determined from the intercept of reduc- Appendix A. Supplementary material
tion peak potential vs. scan rate curve (Fig. 10(b)) by extrapolating
the curve to the potential axis at v ¼ 0. The values of Eo are listed in Crystallographic data for the structure reported in this paper has
Table 5. According to Eq. (6), there is a linear relation between been deposited with the Cambridge Crystallographic Data Centre,
potential (E) and logarithm of scan rate (log v) and the generalized CCDC No. 900473, 891369 and 891370 for NaL and compounds 1
linear regression equation thus obtained is given below: and 2, respectively. Copies of this information may be obtained free
h i of charge from The Director, CCDC, 12, Union Road, Cambridge CB2
Epc ðVÞ ¼ slope  log v Vs1 þ intercept 1EZ [Fax þ44(1223)336-033], e-mail deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk.
The values of ko evaluated using Eq. (6) are given in Table 5
which show that the small sized 4 undergoes more facile elec- References
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