Synthesis of novel bioactive phthalimido-4-methyl pentanoateorganotin(IV) esters with spectroscopic investigation

Article abstract of DOI:10.1016/j.jorganchem.2005.12.031

The synthesis of monomer, dimer, tricyclohexyl- and triphenyl-tin(IV) complexes with phthalimido-4-methyl pentanoic acid (PMPA) are described and characterized by FT IR, CHN analyzer, ¹H, ¹³C ¹¹⁹Sn NMR and ^119mSn M?ssbauer spectroscopic techniques. In vitro ED₅₀, anti-tumor (phytotoxic), anti-yeast, blood pressure and heart rate effect, and bactericidal, fungicidal as well as analgesic bioassays of complexes are also be carried out. The ligand (PMPA) shows excellent analgesic activity while the dimer exhibit strong biocidal and excellent anti-tumor behavior besides of tri-organotin(IV) complexes.

Full text of DOI:10.1016/j.jorganchem.2005.12.031

Journal of Organometallic Chemistry 691 (2006) 1803–1808
www.elsevier.com/locate/jorganchem
Synthesis of novel bioactive phthalimido-4-methyl
pentanoateorganotin(IV) esters with spectroscopic investigation
Muhammad Ashfaq
Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur, Punjab, Pakistan
Received 9 December 2005; accepted 9 December 2005
Available online 28 February 2006
Abstract
The synthesis of monomer, dimer, tricyclohexyl- and triphenyl-tin(IV) complexes with phthalimido-4-methyl pentanoic acid (PMPA)
are described and characterized by FT IR, CHN analyzer, 1H, 13C 119Sn NMR and 119mSn Mo¨ssbauer spectroscopic techniques. In vitro
ED50, anti-tumor (phytotoxic), anti-yeast, blood pressure and heart rate effect, and bactericidal, fungicidal as well as analgesic bioassays
of complexes are also be carried out. The ligand (PMPA) shows excellent analgesic activity while the dimer exhibit strong biocidal and
excellent anti-tumor behavior besides of tri-organotin(IV) complexes.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Phthalimido-4-methylpentanoic acid; Triphenyltin chloride; Tricyclohexyltin chloride; Dibutyltin oxide
1. Introduction
cellular and hormonal immunity; help to transport oxygen
into cells as well prevent lactic acid. The supplements are
used for improvement of behavior, speech and frustration
in children with in 24 h [5,6]. The choice of ligand (PMPA)
is made keeping in view of muscle growth, faster recupera-
tion, and improved performance. The L-leucine is vital for
nitrogen retention in body, and is direct precursor to build-
ing muscle tissue and increasing lean body mass. This is an
extension of our previous work as well as reported by
others on bioactivity and structural chemistry of organo-
tin(IV) complexes [3,4,7–9,11–15]. We also report here
the ED50 (effective dose), anti-tumor (phytotoxic), anti-
yeast, effect on blood pressure and heart rate, bactericidal,
fungicidal as well as analgesic tests besides of the spectral
characterization of the title novel compounds. The com-
plexation of (PMPA) with tin(IV) metal yield products of
exceedingly improved character as powerful biocides.
The di and triorganotin(IV) esters of N-benzoylglycine
have been found to be active in anti-tumor tests against
leukaemia P-388 cells line [1]. Organotin(IV) complexes
of amino acids and their organic derivatives containing
the carboxylic oxygen and tin(IV) bond display significant
anti-tumor activity and promising potential in many other
fields like, pesticidal, bactericidal, fungicidal, anti-fouling,
wood preservation, polymer and paint industries as well
as biomedical fields, etc. [1–8]. The structural chemistry
of di- as well as tri-organotin(IV) complexes of carboxylic
moieties as amino acids and N-protected amino acids with
a coordination number higher than four has significant
potential which have been cited in the literature pertaining
the bioactivity as anti-tumor agents [5–11]. Literature
divulges that the metal complexes were found to be more
potentiated than the parent drugs while the organotin(IV)
esters are exhibited themselves more promising in character
[2,3]. The derivatives of amino acids are used as an antiox-
idant and have shown to have potential in increasing
immune response to the flu and salmonella. They enhance
2. Results and discussion
2.1. Synthesis
The phthalimido-4-methylpentanoic acid (ligand) was
synthesized by fusing of phthalic anhydride and 2-amino-
E-mail address: chmashfaq@yahoo.com.
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.12.031

1804
M. Ashfaq / Journal of Organometallic Chemistry 691 (2006) 1803–1808
4-methylpentanoic acid in an oil bath at 185 °C. The di-n-
butyltin(IV)-di(phthalimido-4-methylpentanoate)tin(IV) and
bis[di-n-butyl(phthalimido-4-methylpentanoate)tin(IV)] ox
ide were synthesized in 2:1 and 1:1 ratio with ligand and
di-n-butyltin(IV) oxide, respectively.
tin(IV) atoms. The 13C NMR signals were properly
resolved, and showed single signal for each methylene car-
bon in butyl group around the tin atom in monomer and a
pair of signals around exo and endo cyclic tin(IV) were
observed in dimer ester. The coupling satellite
nJ(13C–119Sn) at high resolution NMR for the both mono-
mer and dimer compound with well known ranking
[1J] ꢂ [3J] > [2J] was reported in the literature[14,27,28].
The 119Sn chemical shift at ꢃ144.13 ppm of monomeric
type reveals coordination from carboxylic oxygen to tin
center, which suggests the bidentate mode in equatorial
positions with two adjacent short and two longer Sn–O
bonds (Fig. 1). The 119Sn NMR spectrum of dimer type
showed two signals at low and high resonance. The exo
tin(IV) atom may be bonded in monodentate mode with
carboxylic oxygen of ligand. However, the endo cyclic
tin(IV) atom may be bonded in bidentate mode with oxy-
gen of carboxylic groups ligand. This mode of coordination
with exo cyclic tin atoms results in penta coordination, tri-
gonal bi-pyramidal geometry [25]. Such behavior of tetra-
organotin(IV) compounds were reported by Pervez et al.
[6,17,18,21] as centro-symmetric skew trapezoidal bi-pyra-
midal geometry for the endo-cyclic tin status while the
exo-cyclic tin status are in distorted trigonal bi-pyramidal
geometry. The 119mSn Mo¨ssbauer spectra displayed quad-
C8H4O3 þ NH2CH ꢀ R ꢀ COOH
! C8H4O2 ꢀ NCH ꢀ R ꢀ COOH þ H2O
R ¼ ½CH2C6H5ꢁ
ð1Þ
ð2Þ
Bu2SnO þ 2RCOOH ! Bu2SnðOOCRÞ2 þ 2H2O
4Bu2SnO þ 4RCOOH ! ½fBu2SnðOOCRÞg2Oꢁ2 þ 4H2O
ð3Þ
O
R =
13
CH
10
12
11
3
3
N CH CH
CH
2
5
CH
2
3
4
O
Equimolar of triphenyltin(IV) chloride or tricyclohexyl-
tin (IV) chloride and phthalimido-4-methyl pentanoate
sodium were refluxed for 4–5 h in chloroform to prepare
triorganotin(IV)phthalimido-4-methylpentanoate
esters.
The sodium salt of ligand was prepared by shaking of eth-
anolic solution of NaOH and ligand(PMPA) in equimolar
ratio.
rupole splitting values over the range of 3.41 mm sꢃ1
,
RCOOH þ NaOH ! RCOONa þ H2O
R03SnCl þ RCOONa ! R03SnOOCR þ NaCl
ðwhere: R03 ¼ phenyl or cyclohexylÞ
ð4Þ
ð5Þ
which is greater than the 2.1 mm sꢃ1 value reported in
the literature [9,16,29] for a trans octahedral geometry
around tin atom of monomer diorganotin dicarboxylate
complexes Similarly, Gielen et al. [15] reported trans octa-
hedral geometry of monomer type compounds (Fig. 1).
2.2. Spectral studies of mono- and dimer complexes
The large quadrupole splitting value (QS = 3.65 mm sꢃ1
)
of 119mSn Mo¨ssbauer for dimer type compound recom-
mended a penta coordinate environment, which strongly
suggested the tetrabutyl bis(phthalimido-4-methylpentano-
ato) distannoxane dimer type (Fig. 2). The %CHN verified
the monomeric and dimeric composition of compounds 1
and 2 is 2.3.
Spectral studies tri-organotin(IV) complexes. The IR
behavior of carbonyl (CO) found same as reported in the
literature [9,29]. The asymmetric and symmetric stretching
of compounds 3 and 4 were raised and lowered than the
values of sodium salt while Dm in the complexes was also
larger than the Dm in sodium salt of ligand, which indicated
unidentate or weak bidentate bonding to tin(IV) [30,31],
which may easily be identified by given stretching ranks
The OH broad band for ligand disappeared in the com-
plexes. Both asymmetric and symmetric stretching of the
phthalimido (C2O2N) and of the carbonyl (CO) groups
and the stretching for Sn–C and Sn–O were exhibited as
reported in the literature [16–23]. The asymmetric and sym-
metric stretching values of CO groups of monomeric as
well in dimeric type esters were raised and lowered than
the ligand’s values and Dm values of compounds were
higher than the Dm of ligand. The monomeric and dimeric
esters showed bidentate symmetric bonding with tin(IV)
atom, which suggested the octahedral geometry for mono-
meric type and hexa coordinate bonding of carboxylate to
the tin atoms, which are easily be indicated by ranking of
asymmetric and symmetric stretching of CO group of com-
plexes and of ligand [masym(comp.) > masym(ligand),msym(comp.)
< msym(ligand),Dm(compound) > Dm(ligand)]. The butyl protons
in mono- and dimeric types were resolved on a proper posi-
tion as multiplet at room temperature indicating fluxional
behavior [24–26]. The monodentate coordination of car-
boxylic function to tin(IV) atom and in its correspond,
two triplets for the methyl protons of butyl tin in the dimer
compound were reported by Gielen in 1997 and Camacho
et al. in 1999 [14] at very low temperature and high resolu-
tion NMR 500 MHz, which is due to non-equivalent envi-
ronment of methyl protons bonded to endo and exo cyclic
of CO groups between complexes and salt [masym(comp.)
>
m
asym(salt),msym(comp.) < msym(salt),Dm(compound) > Dm(salt)]. The
1H, 13C and 119Sn NMR spectra of the triorgano-
tin(IV)phthalimido-4-methylpentanoate esters were re-
Bu
O
O
O
O
R
Sn
Bu
C R
C
Fig. 1. Trans octahedral geometry.

M. Ashfaq / Journal of Organometallic Chemistry 691 (2006) 1803–1808
1805
Table 1
R
Bu Bu
Anti-yeast bioassay
C
C
O
O
O
Bu
Name of yeast*
Activities
Sn
O
Bu
Bu
O
Sn
O
Sn O
(m). RS 322Y (RAD52)
(w). LF 15 (RAD+)
1
2
3
4
5
Streptonigrin
Bu
O
R
C O
Sn
–
–
+++ +++ ++ +++++
O
O
Bu
1
C
O
C
Key. *, Saccharomyces cerevisiae; ++++, very high activity; +++, high;
++, optimum.
R
Bu
R
CH CH
6
Bu=
CH
CH
9
2
2
3
2
7
8
Fig. 2. Dimeric geometry.
Table 2
Analgesic activity on albino mice
corded. The expected shifting was assigned by their multi-
plicity and intensity pattern. Based on the literature, [3,8] it
is suggested that the complexes have tetrahedral geometry.
The 119Sn NMR signals were seen over the range of
ꢃ121.17 ppm for triphenyl and 74.43 ppm for the tri-cyclo-
hexyl moieties bonded to Sn(IV). It recommended a penta
coordinate environment around tin(IV) atom, which sug-
gested that the triphenyltin(IV) ester leaded to a polymeric
trigonal bi-pyramidal in the solid and a tetrahedral geom-
etry in an inert solvent while tricyclohexyltin(IV) com-
pound exhibited tetrahedral geometry in the solid as well
as in solution [31]. Based on evidences, their structures
are displayed in Figs. 3 and 4.
Dosage (mg/kg) No. of writhes % Inhibition by compounds
1
2
5
Aspirinb
Controla
10
48
–
–
5(2)
–
7(3)
–
–
–
–
20(10)
50
–
55(26) 57(27) 54(26)
64(31) 63(30) 70(34)
–
100
–
150
–
–
67
Note. Writhes remained are given in parentheses
a
Acetic acid.
Standard drug.
b
The compounds 3 and 4 showed the highest toxicity
against brine shrimp larvae and in vitro phytotoxic anti-
tumor activity against Lemna acquinoctialis welv (Tables
3, 4) [32–36]. Both the di- and tri-organotin complexes
(1–4) exhibited bactericidal and fungicidal properties
(Tables 5, 6). Triorganotin(IV) class is significantly active
than other classes since having a greater partition coeffi-
cient value [18]. It may also be considered the presence
of lone pair on oxygen of carbonyl of ligand is not
involved in coordination process, which may play a key
role to increase the toxicity. Such trend was not observed
in mono and dimer types since the lone pair may actually
be bounded through a weak/strong bidentate bonding.
Moreover, toxicity is also confined with an attached ‘‘R’’
group to tin(IV) atom. In the R3SnL unit, the function
of L (ligand) plays a key role in transporting the active
site of organotin(IV) moiety, which is released on hydro-
lysis [1,35,36]. Among such compounds, the carboxylate
derivatives are used as anticancer and anti-tumor agents
in vivo as well as in vitro fungicides or bactericides
[37,38]. The biocide activity of triorganotin(IV) motifs is
enhanced on account of their geometry in solution. The
tetrahedral structure in solution is more active than other
forms. It is also reported in the literature [39–41] that the
The 119mSn Mo¨ssbauer spectra of triphenyl- and tricy-
clohexyl-tin(IV) phthalimido-4-methylpentanoate have
quadrupole splitting values of 3.42 and 2.73 mm sꢃ1
,
respectively. According to a literature [3,19,29,30] the com-
pounds with 3.59–3.70 mm sꢃ1 QS values have a five-coor-
dinate chain structure and the complexes with 3.39 mm sꢃ1
QS value displayed a tetrahedral in solid and trigonal bi-
pyramidal geometry with a bridging carboxyl group in an
inert solvent, where d = QS/IS also supports the same
geometry [9,30].
2.3. Biological activities
The ligand and the compounds 1 and 2 at the doses of
10, 20 and 40 mg/kg body weight showed no effect on
blood pressure and heart rate of animal as well as no activ-
ity was found towards the yeasts. The compounds 5
(ligand), 1 and 2 exhibited an excellent analgesic activity.
The results can be viewed in Tables 1, 2.
R
O
Sn
C
R
O
R
R
Table 3
Fig. 3. Tetrahedral geometry.
Brine shrimp bioassay
Compounds % Deaths at doses
1000 lg/ml 100 lg/ml 10 lg/ml
ED50 lg/ml Results
R
6
Sn
O
6
9
O
7
8
1
2
3
4
35
30
100
100
12
10
100
95
9
10
80
90
1
ꢃ
7
8
or
C
R =
R
R
1
ꢃ
9
R
3.85
0.0085
++++
++++
n
3
4
Fig. 4. Polymeric trigonal bi-pyramidal geometry.
Key. ++++, more significant; ꢃ, no activity.

1806
M. Ashfaq / Journal of Organometallic Chemistry 691 (2006) 1803–1808
Table 4
Table 6
Invitro phytotoxic (anti-tumor) bioassay of Lemna acquinoctialis welv
Fungicidal bioassay
Compounds Dose
(lg/ml)
No. of fronds
% Growth F1 50a
regulation (lg/ml)
Name of fungi
Activitya of compounds
Experimental Control
1
2
3
4
1
2
3
4
500
50
5
00
00
8
11
9
9
100
100
20
0.0000
0.125
Aspergillus flame
–
–
++++ ++++
(human pathogens)b
Trichophyton schoenlem
Pseudallescheria boydii
Candida albicans
++
++
+
++
++
+
++++ ++++
++++ ++++
++++ ++++
++++ ++++
500
50
5
00
00
8
11
9
10
100
100
20
0.0000
0.125
Aspergillus nigerc
+
+
Animal pathogensb
Microsporum canis
Trichophyton mantagrophytes
Trichophyton rubrum
Trichophyton
500
50
5
00
00
00
11
11
11
100
100
100
0.0000
0.125
ꢃ
ꢃ
ꢃ
ꢃ
+++
ꢃ
+++
ꢃ
++++ ++++
ꢃ
ꢃ
+++
+++
++++ ++++
500
50
5
00
00
00
11
11
11
100
100
100
0.0000
0.125
Plant pathogensd
Fusanum oxysponumvarlycopersici ++++ ++++ ++++ ++++
a
Concentration used to inhibit and promote 50% of frond proliferation.
Fusanum solanivarlycopersici
Macrophormina phaseolina
Rhizoctonia solani
++++ ++++ ++++ ++++
++++ ++++ ++++ ++++
ꢃ
Reference inhibitor: Praqual 100%.
ꢃ
ꢃ
ꢃ
Incubation time = 7 h, 27 °C. Reference Drug: bMiconazole, Ketocon-
c
azole; Amphotenicin-B, Flycytosine; dBenlate, Nabam.
four-coordinated species has stronger tendency to increase
the coordination numbers by O, S, or N donor groups
while the five-coordinate species do not undergo further
coordination which play no long-term role in vivo chemistry
of organotin(IV) esters.
a
++++, highest; +++, high; ++, optimum; + and ꢃ, no activity.
3.2. Physical measurements
The melting points of all compounds were measured on a
Reichert thermovar of F.G. Bode Co. Austria. The Perkin–
Elmer FTIR-1605 was used with KBr disc for IR analysis.
Elemental analyses were carried out on a Yanaco MT-3
high-speed CHN analyzer with an antipyrene reference com-
pound. The 1H, 13C and 119Sn NMR spectra were recorded
on a multinuclear FT NMR 200 MHz of JEOL using TMS
at room temperature. Some of the 13C spectra were measured
on a Bruker AM 270 instrument at 50 MHz with 13C probe.
The 119Sn NMR spectra were obtained on a Bruker WM 500
instrument at 93.1 MHz. The 119mSn Mo¨ssbauer spectra
were recorded on a V.G.Micromass 7070 F instrument at a
temperature of 200 °C. The ED50 of the complexes was deter-
mined against a brine shrimp hatching method while bacte-
ricidal and fungicidal activity was measured by agar-well
diffusion and agar-tube dilution methods [25,26] In vitro
phytotoxic anti-tumor activity tests (potato disc assay) were
carried out using 10 plants of Lemna acquinoctialis welv for
the purpose [24,25]. The anti-yeast bioassay of ligand and the
organotin compounds against mutant (Saccharomyces cere-
visiae, Rs 322Y RAD52) and wild types strains (S. cerevisiae
LF15RAD+) was determined. Streptonigrin was used as a
standard drug. Effect of compounds on blood pressure and
heart rate were checked using Sprague Dawely wistars rats.
SathamP23 coupled with 79-Polygraph was used for the pur-
pose and normal response was found against acetylcholine
and noradrenaline (hypertensive) as standard drugs. Albino
mice were under the experiments for an analgesic activity test
and number of writhing response for each mouse was
recorded using aspirin as a standard. Acetic acid was used
for writhing response. Intraperitoneal rout was used for dose
administration [39,40].
3. Experimental
3.1. Materials
Phthalic anhydride, 2-amino-4-methylpentanoic acid,
dibutyltin(IV) oxide, tri- phenyltin(IV) chloride and tricy-
clohexyltin(IV) chloride were commercially available from
Merck Chemicals Co. Ltd. and were used without further
purification. The ligand was prepared according to a
reported procedure [21]. All the complexes were prepared
according to reported procedures [8,9]. They were soluble
in chloroform and ethanol (on heating) and insoluble in
methanol and water.
Table 5
Bactericidal bioassay
Name of bacteria
(human pathogens)
Activitya of compounds
1
2
3
4
Bacillus cereus
++++ ++++ ++++
++++
Cornye bacterium diphtheriae ++++ ++++ +++++ +++++
Escherichia coli ETEC.
Klebsiella pneumoniae
Salmonella typhi
++
++
+
++
++
+
++++
++++
++++
++++
ꢃ
++++
++++
++++
++++
ꢃ
Staphylococcus aureus
Shigella boydii
+++
ꢃ
+++
ꢃ
Pseudomons aeroginosa
Proteus mirabillis
Streptococcus pyogenes
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
+++
+++
++++
++++
Reference drug: Amoxicillin (H2O), Ampicillin (H2O), Cephlaxin Na.
Incubation period: 8 h, 37 °C; colony forming unit = 104–106; size of
well = 5 mm radius.
a ++++, highest; +++, high; ++, optimum; + and ꢃ, no activity.

M. Ashfaq / Journal of Organometallic Chemistry 691 (2006) 1803–1808
1807
3.3. Synthesis and characterization
FT IR analysis (cmꢃ1): C2O2N (phthalimido): 1772asym
sp, 1715sym s.sp; CO (carbonyl): 1670asym s, 1387sym s; Dm:
283; Sn–C: 541 sp; Sn–O: 513 w.
3.3.1. Compound 1
{C6H4(CO)2N{CHCH2CH(CH3)2}COO}2SnBu2
Re-crystallized from chloroform, m.p.: 204 °C, yield
81%, solubility: soluble in chloroform, soluble in ethanol
on heating, slightly soluble in methanol and insoluble in
water, when fourfold of water was added its alcoholic solu-
tion remained clear.
119mSn Mo¨ssbauer data (mm sꢃ1): QS, 3.42; IS, 1.6; G1,
0.84; G2, 0.81; d = QS/IS: 2.14.
1H NMR (CDCl3): H-4, 7.73 d (8); H-5, 7.53 d (8); H-7,
7.31–7.34 m; H-8/9, 7.48–7.52 m; H-10, 5.02 dd (4, 4, 3); H-
11, 2.42–2.02 m; H-12, 1.42–1.28 m; H-13, 0.99 d (8).
13C NMR (CDCl3): C-1, 172.3; C-2, 167.8; C-3, 131.1;
C-4, 123.3; C-5, 133.8; C-6, 135.0; C-7, 124.0; C-8, 129.1;
C-9, 133.8; C-10, 51.7; C-11, 38.3; C-12, 25.6; C-13, 21.3.
119Sn NMR (CH3)4Sn: ꢃ121.17.
CHN analysis (%) antipyrene: C, 57.25 (57.37); N, 3.75
(3.74); H, 5.21 (5.11); the calculated values are in the
parentheses.
FT IR analysis (cmꢃ1): C2O2N (phthalimido): 1775asym
sp, 1721sym s.sp; CO(carbonyl): 1639asym sp, 1383sym sb;
Dm: 256; Sn–C: 545 w.sp; Sn–O: 486 sp.
3.3.4. Compound 4
[(C6H11)3SnOOCCHCH2CH(CH3)2N(CO)2C6H4]
Solidified from n-hexane, m.p.: 145–147 °C, yield: 89%,
solubility: soluble in chloroform, soluble in ethanol on
heating, slightly soluble in methanol but insoluble in water.
When sixfold water was added its alcoholic solution
remained clear.
119mSn Mo¨ssbauer data (mm sꢃ1): QS: 3.41; IS: 1.35;
G1: 1.18; G2: 1.17; d = QS/IS: 2.53.
1H NMR (CDCl3): H-4, 7.83 d (8); H-5, 7.59 d (8); H-6,
1.64 t (7); H-7, 1.52–1.61 m; H-8, 1.33–1.10 m; H-9, 0.91;
H-10, 4.74 dd (6,6,5); H-11, 2.35 t (ꢄ7); H-12, 1.81–1.85
m; H-13, 0.78 d (8).
CHN analysis (%): C, 61.09 (61.16); N, 7.50 (7.54); H,
2.19 (2.22).
13C NMR (CDCl3): C-1, 176.3; C-2, 166.8; C-3, 132.5;
C-4, 123.2; C-5, 133.7; C-6, 27.3; C-7, 27.7; C-8, 23.1; C-
9, 13.4; C-10, 52.5; C-11, 38.1; C-12, 27.9; C-13, 21.2.
119Sn NMR (CH3)4Sn: ꢃ144.13.
FT IR analysis (cmꢃ1): C2O2N (phthalimido): 1772asym
sp, 1702sym sb; CO(carbonyl): 1665asym s.sp, 1387sym s.sp;
Dm: 278; Sn–C: 543 sp; Sn–O: 513 w.
119mSn Mo¨ssbauer data (mm sꢃ1): QS, 2.73; IS, 1.45;
G1, 0.98; G2, 1; d = QS/IS: 1.88.
3.3.2. Compound 2
1H NMR (CDCl3): H-4, 7.74 d (8); H-5, 7.55 d (8); H-6,
1.47; H-7-9, 1.44–1.52 m; H-10, 3.96 d (8.5); H-11, 2.89; H-
12, 2.87–1.88 m; H-13, 0.85 d (8).
[C6H4(CO)2N{CHCH2CH(CH3)2COOSnBu2}2O]2
Re-crystallized from chloroform, m.p.: 212 °C, yield:
89%, solubility: soluble in CHCl3, soluble in ethanol on
heating, slightly soluble in methanol and insoluble in water.
CHN analysis (%) antipyrene: C, 52.55 (52.72); N, 2.79
(2.81); H, 6.23 (6.24).
13C NMR (CDCl3): C-1, 178.3; C-2, 167.5; C-3, 132.8;
C-4, 123.6; C-5, 133.4; C-6, 35.3; C-7, 31.07; C-8, 29.1;
C-9, 28.4; C-10, 60.5; C-11, 27.7; C-12, 28.9; C-13, 22.6.
119Sn NMR (CH3)4Sn: 74.43.
FT IR analysis (cmꢃ1): C2O2N (phthalimido): 1774asym
sp, 1720sym s.sp; CO(carbonyl): 1640asym sp, 1385sym sb;
Dm: 255; Sn–C: 545 w.sp; Sn–O: 487 sp.
3.3.5. Compound 5 ligand:
119mSn Mo¨ssbauer data (mm sꢃ1): QS, 3.65; IS, 1.32;
G1, 0.84; G2, 0.82; d = QS/IS: 2.77.
[C6H4(CO)2N{CH Æ CH2CH(CH3)2}COOH]
Re-crystallized from 10% ethanol, m.p.: 118 °C, yield
94%, solubility: soluble in ethanol and methanol, insoluble
in chloroform and water.
1H NMR (CDCl3): H-4, 7.80 d (8); H-5, 7.71 d (8); H-6,
1.50 t (7); H-7, 1.44–1.48 m; H-8, 1.20–1.25 m; H-9, 0.94;
H-10, 4.82 dd (5,5,4); H-11, 2.39 t (ꢄ7); H-12, 1.85–1.89
m; H-13, 0.69–0.74 m.
CHN analysis (%) antipyrene: C, 57.33 (57.37); N, 3.72
(3.74); H, 5.10 (5.11).
13C NMR (CDCl3): C-1, 175.7; C-2, 167.6; C-3, 133.4;
C-4, 123.9; C-5, 134.0; C-6, 27.1/ 28.5; C-7, 26.6/ 26.8; C-
8, 23.02/24.2; C-9, 13.1; C-10, 52.3; C-11, 37.8; C-12,
26.9; C-13, 21.1.
FT IR analysis (cmꢃ1): OH (acidic) 3435–3243 b,
C2O2N (phthalimido): 1785asym m.b, 1713sym s.b; CO (car-
bonyl): 1639asym m.b, 1393sym s.sp; Dm: 222.
119Sn NMR (CH3)4Sn: ꢃ199.50, ꢃ208.51.
3.3.6. Compound 6 sodium salt of ligand:
[C6H4(CO)2N{CHÆCH2CH(CH3)2}COONa]
Re-crystallized from water, m.p.: >300 °C, yield 96%,
solubility: soluble in water slightly soluble in ethanol and
methanol and insoluble in chloroform.
3.3.3. Compound 3
[(C6H5)3SnOOCCHCH2CH(CH3)2N(CO)2C6H4]
Solidified from n-hexane, m.p.: 145–147 °C, yield: 89%,
solubility: soluble in chloroform, soluble in ethanol on
heating, slightly soluble in methanol and insoluble in water.
When sevenfold of water was added its alcoholic solution
remained clear.
CHN analysis (%) antipyrene: C, 53.34 (53.36); N, 4.92
(4.94); H, 4.93 (4.94).
FT IR analysis (cmꢃ1): OH (acidic) band disappeared,
C2O2N (phthalimido): 1774asym s.sp, 1728sym s.sp; CO-
(carbonyl): 1587asym, 1431sym s.sp; Dm: 156. (s = strong,
sp = sharp, b = broad, w = weak).
CHN analysis (%) antipyrene: C, 62.95 (62.98); N, 4.72
(4.79); H, 2.25 (2.30).

1808
M. Ashfaq / Journal of Organometallic Chemistry 691 (2006) 1803–1808
Acknowledgements
B. Furniss, A.J. Hannaford, P.W.G. Smith, A.R. Tatchell, Vogel’s
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Sadtler Standard Spectra, Midgot Edition, Sadtler Research Labo-
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344, 417.
Thanks to NCE in Analytical Chemistry, Sindh Univer-
sity, Jamshoro and HEJ Research Institute, University of
Karachi, for spectroscopic analysis and for bioactivities
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