Synthesis, spectral (FT-IR, 1H, 13C, 119Sn) and biological studies of bimetallic trimethyltin(IV) germapropionates: X-ray structure of (CH3)3Sn(C22H21O2Ge)

Article abstract of DOI:10.1080/15533170701301470

New compounds of bimetallic trimethyltin(IV) germapropionates have been synthesized and characterized by elemental analyses, FT-IR, and multinuclear nmr (1H,13C,119Sn) spectroscopies. These compounds show four-coordinated structure in solution and penta-coordinated structure in solid state. The crystal structure of representative compound, (CH3)3Sn(C22 H21 O2 Ge), shows one dimensional polymeric penta-coordinated structure in its solid state. The synthesized compounds were subjected for a bioassay screening and show promising antibacterial and antifungal activitie.

Full text of DOI:10.1080/15533170701301470

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Synthesis, Spectral (FT‐IR, 1H, 13C, 119Sn) and
Biological Studies of Bimetallic Trimethyltin(IV)
Germapropionates: X‐Ray Structure of
(CH3)3Sn(C22H21O2Ge)
Muhammad Kaleem Khosa a , Muhammad Mazhar b , Saqib Ali b , Sarim Dastgir b , Masood
Parvez c & Abdul Malik d
a Department of Chemistry , Government College University , Faisalabad, Pakistan
b Department of Chemistry , Quaid‐i‐Azam University , Islamabad, Pakistan
c Department of Chemistry , University of Calgary , Calgary, Alberta, Canada
d HEJ Research Institute of Chemistry, International Center for Chemical Sciences, University
of Karachi , Karachi, Pakistan
Published online: 24 Apr 2007.
To cite this article: Muhammad Kaleem Khosa , Muhammad Mazhar , Saqib Ali , Sarim Dastgir , Masood Parvez & Abdul Malik
(2007) Synthesis, Spectral (FT‐IR, 1H, 13C, 119Sn) and Biological Studies of Bimetallic Trimethyltin(IV) Germapropionates: X‐Ray
Structure of (CH3)3Sn(C22H21O2Ge), Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 37:3,
165-173
To link to this article: http://dx.doi.org/10.1080/15533170701301470
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Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 37:165–173, 2007
Copyright # 2007 Taylor & Francis Group, LLC
ISSN: 1553-3174 print/1553-3182 online
DOI: 10.1080/15533170701301470
Synthesis, Spectral (FT-IR, 1H, C, 119Sn) and Biological
13
Studies of Bimetallic Trimethyltin(IV) Germapropionates:
X-Ray Structure of (CH3)3Sn(C22H21O2Ge)
Muhammad Kaleem Khosa
Department of Chemistry, Government College University, Faisalabad, Pakistan
Muhammad Mazhar, Saqib Ali, and Sarim Dastgir
Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan
Masood Parvez
Department of Chemistry, University of Calgary, Calgary, Alberta, Canada
Abdul Malik
HEJ Research Institute of Chemistry, International Center for Chemical Sciences, University of Karachi,
Karachi, Pakistan
may eventually enter the human food chain, accumulate
New compounds of bimetallic trimethyltin(IV) germapropio- in the environment and finally in the biological system.[6]
nates have been synthesized and characterized by elemental
analyses, FT-IR, and multinuclear nmr (1H,13C,119Sn) spectrosco-
pies. These compounds show four-coordinated structure in
The biological importance of organotins has been supported
by studies concentrating on structure-activity correlations[7,8]
and it has been observed that several diorganotin and trior-
solution and penta-coordinated structure in solid state. The
crystal structure of representative compound, (CH3)3Sn(C22 H21
ganotin species show potential as anti-neoplastic agents.[9]
O2 Ge), shows one dimensional polymeric penta-coordinated Triorganotin compounds demonstrate an interesting range
structure in its solid state. The synthesized compounds were sub-
jected for a bioassay screening and show promising antibacterial
and antifungal activities.
of structural variations leading to an indefinite structure cor-
relation with biocidal activity.[10] Organogermanium is
another kind of compound that has a wide range of
biocidal applications.[11]
It has been reported that triorganotin carboxylates con-
taining the biologically active germyl group in the carboxy-
Keywords organotin, carboxylates, germanium, X-ray studies, bio-
logical studies
late ligand, exhibit good acaricidal activity. Biological
testing of germanium-tin compounds has demonstrated that
these compounds can be used against bacterial, viral and
INTRODUCTION
antifungal ailments found in both humans and in animals.
In the past two decades, organotin chemistry has
Some of these compounds were found to be more active
received much attention because of its extensive appli-
for certain bacteria than the reference drug.[12] To link
cations in different fields of life especially industrial, agri-
biological properties of organotin and organogermanium
cultural and biocidal applications.[1–5] The use of
compounds, we have synthesized some new triorganotin car-
inorganic tin, considered the third most pollutant element
boxylates containing triorganogermyl group as a part of the
in the ecosystem, has increased general concern that it
carboxylate ligand and report their antibacterial and antifun-
gal activities. In parallel, we also studied the nature of
bonding and structure of these compounds in solution as
Received 27 November 2006; accepted 15 January 2007.
We thank the Higher Education Commission, Islamabad, Pakistan
well as in solid state. The general synthetic procedure, struc-
for their financial support. (Grant No. 20-9/Acad-R/2003).
tural characterization using variety of spectroscopic tech-
Address correspondence to Muhammad Kaleem Khosa, Depart-
niques (1H,13C,119Sn) and crystal structure of representative
ment of Chemistry, Government College University, Faisalabad,
Pakistan. E-mail: mkhosapk@yahoo.com.
compound (1) are reported here.
165

166
M. K. KHOSA ET AL.
EXPERIMENTAL
reaction between magnesium (0.176 mole) and bromoben-
zene/p-bromotoluene (0.16 mol) in THF (30 cm3) under
nitrogen. The resulting Phenyl/p-tolyl magnesium bromide
was added drop wise at 08C to 3-(trichlorogermyl) substi-
tuted propionic acid (0.04 mole) in THF. After the
addition, the mixture was refluxed for 4 hours. Reaction
mixture was cooled and 10% aqueous hydrochloric acid
was added. The water phase was extracted three times
with chloroform. The chloroform phase was dried over
anhydrous magnesium sulfate and filtered. The solvent
was removed under vacuum to give white solid. The solid
was then recrystallized from chloroform and acetone (3:1)
to obtain a colorless crystalline solid.
Chemicals
Trimethyltin chloride, substituted cinnamic acids were pur-
chased from Aldrich Chemicals (USA) and Germanium
dioxide (99.9% purity) was purchased from the People’s
Republic of China and was used without further purification.
All organic solvents were purchased from E-Merk, Germany
and were dried over sodium benzophenone before use accord-
ing to the standard method.[12]
Instrumentation
Elemental analyses were carried out at Midwest MicroLab
Indianapolis, USA. Melting points were determined with
Mitamura Riken Kogyo (Japan). IR was recorded on Bio-Rad
Excalibure FT-IR Model FTS 3000 MX using KBr disc. The
1H and 13C NMR spectra were recorded on Varian Mercury
300 spectrometer using deuterated solvents and TMS as a refer-
ence operating at 300 and 75.5 MHz, respectively. 119Sn NMR
spectra were obtained on Bruker 250 ARX spectrometer
(Germany) with TMS as a reference. The crystallographic
data were collected at 173K on Nonius Kappa CCD diffract-
ometer and the crystals suitable for X-ray diffraction were
isolated from solution of chloroform and acetone mixture
(3:1) over a prolonged period at room temperature.
Synthesis of Title Compounds
Title compounds were synthesized according to the litera-
ture method.[13] Equimolar of triarylgermyl substituted propio-
nic acid and trimethyltin(IV) chloride was refluxed for 8–
10 hours in toluene (50 cm3) in the presence of triethylamine.
Reaction mixture was cooled down, filtered and the solvent
was removed under reduced pressure. Recrystallization of
resulting solid was taking placed from a mixture of chloroform
and acetone (3:1) yielded fine crystals.
Biological Studies
The synthesized compounds (1–10) were evaluated for
their antibacterial activity by agar well diffusion
method[13] against six different types of bacteria. The
bacteria cultures used were Escherichia coli, Bacillus
Synthesis
Synthesis of Triarylgermyl Substituted Propionic Acids
The 3-(triarylgermyl) substituted propionic acids were subtilis, Shigella flexenari and Salmonella typhi. Imipenum
synthesized according to the reported procedure.[12] was used as standard antibiotic. The 24-hours-old culture
Phenyl/p-tolyl magnesium bromide was prepared by containing approximately 104–106 colony forming unit
TABLE 1
Physical data of triorganotin derivatives of general formula: ((R1)3 Ge CH (R2) CH2COO) Sn (CH3)3
Elemental analysis found
(Calcd.)
Molecular
formula
Comp.
R1
C6H5
R2
M. Wt.
M.P.8C
Yield%
C%
H%
1
2
CH3
C6H5
o-CH3OC6H4
C25H30O2GeSn
C30H32O2GeSn
C31H34O3GeSn
554
616
646
646
630
651
688
688
688
658
672
178–180
134–136
165–168
140–143
165
59
63
64
62
76
85
81
84
79
83
76
54.05 (54.15)
58.50 (58.44)
57.61 (57.58)
57.52 (57.58)
58.97 (59.04)
55.30 (55.29)
59.29 (59.30)
59.31 (59.30)
59.28 (59.30)
60.10 (60.18)
60.74 (60.71)
5.40 (5.41)
5.16 (5.19)
5.21 (5.26)
5.23 (5.26)
5.34 (5.39)
4.77 (4.76)
5.79 (5.81)
5.82 (5.81)
5.79 (5.81)
5.76 (5.77)
5.93 (5.95)
C6H5
C6H5
3
4
C6H5
C6H5
C6H5
m-CH3OC6H4 C31H34O3GeSn
5
p-CH3C6H4
p-ClC6H4
o-CH3OC6H4
C31H34O2GeSn
C30H31O2GeSnCl
C34H40O3GeSn
6
182–184
133–135
142–143
161–162
178–180
181–182
7
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
8
m-CH3OC6H4 C34H40O3GeSn
9
p-CH3OC6H4
C6H5
p-CH3C6H4
C34H40O3GeSn
C33H38O2GeSn
C34H40O2GeSn
10
11

BIMETALLIC TRIMETHYLTIN(IV) GERMAPROPIONATE SYNTHESIS
167
TABLE 2
Characteristics IR absorption frequencies in cm21 of triorganotin(IV) derivatives of general formula:
((R1)3 Ge CH (R2) CH2COO) Sn (CH3)3
Comp.
n(COO)asym
n(COO)sym
Dn
n(Ge-C)
n(Sn-C)
n(Sn-O)
1
2
1680
1678
1685
1682
1679
1690
1688
1683
1697
1690
1682
1440
1443
1452
1458
1457
1453
1459
1457
1466
1452
1454
240
235
233
224
222
237
229
226
231
238
228
650
656
665
658
655
648
658
664
667
674
664
545
549
562
549
551
552
562
552
554
561
552
462
465
460
465
468
462
469
468
466
465
462
3
4
5
6
7
8
9
10
11
˚
(CFU) was spread on the surface of Muller Hinton Agar with (graphite monochromater, l ¼ 0.71073A). The data
(MHA) plates. Wells were created in medium with the were corrected for Lorentz and polarization effects for
help of a sterile metallic borer. Test samples of different absorption, using the multi-scan method. The details of
concentrations were added in their respective wells. Exper- crystal data and structure refinement have been included
imental plates were incubated at 378C for 24 hours and here 5. The structure was solved by direct method and
zones of inhibition (%) were measured and compared with refined by full-matrix least squares procedure using
standard antibiotic imipenum with zone inhibition of 20 SHELXL-97.[13] The hydrogen atoms were included at geo-
and 22 mm, respectively.
metrically idealized positions.
The agar tube dilution protocol[13] was applied to study the
activity of the compounds against various fungal strains such as
Trichophyton longifusus, Candida albicans, Aspergillus flavus,
Microsporum canis, Fusarium solani and Candida glaberata.
The standard antifungal drugs used were Amphotericin B and
Micronazole for comparison test. The tubes containing sterile
sabour and dextrose agar were incubated with the test
compound at different concentrations and solidified at room
temperature. Test fungal cultures were inoculated on the
slant, and growth inhibition (%) was observed after an incu-
bation period of 7 days.
RESULTS AND DISCUSSION
Triorganotin (IV) derivatives containing germanium
have been synthesized by the reaction of germanium-sub-
stituted carboxylic acid with trimethyltin chloride in (1:1)
molar ratio in dry toluene (50 cm3) in the presence of tri-
ethylamine. However, a prolonged refluxion (8–10 hours)
is required for good yield.[13] The general reaction
The shrimp larvae were applied as a tool to monitor the
cytotoxicity of samples using Etoposide as standard cytotoxic
drug.[13] Brine Shrimp eggs (50 mg) were placed in a
hatching tray half-filled with brine solution and incubated for
2 days at 278C. Test samples (20 mg) was dissolved in
DMSO and diluted to 1000 mg/ mL, 100 mg/ mL,
10 mg/ mL in 500 mL, 50 mL and 5 mL vials using Pasteur
pipettes. Then 30 larvae were placed in each vial and 5 mL
volume was made with seawater. The contents were incubated
at 25–278C for 24 hours under illumination. The number of
survivors were counted and compared with standard cytotoxic
drug.
X-Ray Crystallography
Intensity data for a colorless crystal (0.20 ꢀ 0.16 ꢀ 0.10 mm3)
FIG. 1. Different structure of triorganotin(IV) compounds.
were measured at 295(2)K on Nonius Kappa CCD diffractometer

168
M. K. KHOSA ET AL.
TABLE 3
1H NMR dataa–e for triorganotin derivatives of general formula: ((R1)3Ge CH (R2) CH2COO) Sn (CH3)3
C-Sn-C
angle (8)
Comp.
CH
CH2
R1
R2
Sn-CH3
2
0.58 J[58]
1
2
3
3.15–3.61 (m,1H)
3.42–3.51 (m,1H)
3.71–3.8 (m,1H)
2.41–2.58 (m,2H) 7.3–7.61 (m,15H)
2.54–2.61 (m,2H) 6.65–7.21 (m,15H)
2.58–2.61 (m,2H) 6.25–7.1 (m,15H)
1.35 (d,6.98)
111.0
112
111
2
0.15 J[59]
6.65–7.21 (m,5H)
6.25–7.1 (m,4H)
2.95 (s,3H)
0.10 2J[58.5]
0.15 2J[58]
4
5
3.41–3.62 (m,1H)
3.79–3.81 (m,1H)
2.65–2.81 (m,2H) 6.95–7.21 (m,15H)
2.53–2.64 (m,2H) 6.91–7.65 (m,15H)
6.45–6.65 (m,4H)
3.51 (s,3H)
111
111
6.91–7.65 (m,4H)
2.41 (s,3H)
0.59 2J[58.7]
2
0.81 J[58.6]
0.16 2J[58.2]
6
7
3.61–3.63 (m,1H)
3.31–3.41 (m,1H)
2.51–2.60 (m,2H) 6.27–7.14 (m,15H)
2.61–2.67 (m,2H) 6.80–7.51 (m,12H)
2.10 (s,9H)
6.56–6.65 (m,4H)
6.38–6.46 (m,4H)
3.24 (s,3H)
111
111
8
9
3.38–3.40 (m,1H)
3.41–3.45 (m,1H)
2.65–2.75 (m,1H) 6.82–7.14 (m,12H)
2.15 (s,9H)
6.3–6.51 (m,4H)
3.21 (s,3H)
0.15 2J[59]
112
112
111
112
2.61–2.67 (m,2H) 6.86–7.11 (m,12H)
2.05 (s,9H)
6.31–6.67 (m,4H)
3.51 (s,3H)
6.95–7.41 (m,5H)
0.15 2J[59.5]
0.15 2J[58.1]
0.14 2J[59.8]
10
11
3.52–3.77 (m,1H)] 2.46–2.71 (m,2H) 6.95–7.41 (m,12H)
2.45 (s,9H)
3.45–3.57 (m,1H)
2.61–2.28 (m,2H) 6.61–7.15 (m,12H)
2.15 (s,9H)
6.61–7.15 (m,4H)
2.01 (s,3H)
aIn CDCl3 at 295 K.
bChemical shift in ppm 2J[119Sn 2 1H] in Hz.
cMultiplicity is given as s ¼ singlet, t ¼ triplet, m ¼ multiplet.
dR1 ¼ C6H5 for compounds (1-6), p-CH3C6H4 for (7–11).
eR2 ¼ CH3 (1), C6H5 (2,10), o-CH3OC6H4(3,7), m-CH3OC6H4 (4,8), p-CH3C6H4 (5,11), p-ClC6H4 (6), p-CH3OC6H4 (9).
scheme is shown as the following.
triorganotin carboxylates adopt a three structural motifs in its
solid state[16] as shown in Figure 1. The mode of coordination
of the carboxylate group has been related to the magnitude of
the separation (Dn) of the n(COO)asy and n(COO)sym
vibrations.[15,17] The Dn, which indicates the coordination
number around the tin, in all complexes increased by over
200 cm21 and this was characteristic of a structural change
wherein the carboxylate group passes from the zwitterionic
COO21 form in free ligand[18,19] to ester type O-C55O form
after organotin coordination resulting in a five-coordinate poly-
meric structure[20] as confirmed from the crystal structure of
compound (1).
Et3N
ðR1Þ3GeCHðR2ÞCH2CO2H þ ðCH3Þ3SnCl ꢁ! ðR1Þ3
GeCHðR2ÞCH2CO2SnðCH3Þ3 þ Et3N.HCl
R1 ¼ C6H5ð1 ꢁ 6Þ; p ꢁ CH3C6H4ð7–11Þ
R2 ¼ CH3ð1Þ; C6H5ð2; 10Þ; o ꢁ CH3OC6H4ð3; 7Þ;
m ꢁ CH3OC6H4ð4; 8Þ; p ꢁ CH3C6H4ð5; 11Þ;
p ꢁ ClC6H4ð6Þ; p ꢁ CH3OC6H4ð9Þ
Toluene
All the compounds are solid, which are stable in light and
dry air. They are soluble in organic solvents such as CHCl3,
CH2Cl2, C6H6 and DMSO. The analytical and physical data
of the synthesized compounds are given in Table 1.
1H NMR Spectroscopy
1
The H NMR data of the compounds is given in Table 3.
The expected resonances are ascribed by their multiplicity,
intensity pattern, integration, coupling constant and tin satel-
INFRARED SPECTROSCOPY
The infrared spectra of synthesized compounds have been lites. All the protons in the compound have been identified
recorded in the range of 4000–400 cm21 and the main and total numbers of protons calculated from the integration
spectral data is listed in Table 2. Tentative assignments of curve are in agreement with the expected molecular
1
C55O, Sn-C, Sn-O and Ge-C bonds have been made on the composition. The H NMR data show a well-defined singlet
basis of earlier publications.[14,15] It is well established that in the region 1.0 to 20.81 ppm for methyl protons directly

BIMETALLIC TRIMETHYLTIN(IV) GERMAPROPIONATE SYNTHESIS
169
TABLE 4
13C NMR dataa–e for triorganotin derivatives of general formula ((R1)3 Ge CH (R2) CH2 COO) Sn (CH3)3
Comp.
no.
1
2
3
4
5
6
7
8
9
10
11
R1-Ge
1
138.04
137.53
130.13
132.61
—
138.0
134.42
128.56
130.50
—
138.00
134.51
129.10
131.46
—
138.5
134.1
128.41
129.50
—
137.81
136.12
128.79
131.80
—
137.42
136.84
128.91
132.30
—
140.51
138.24
128.61
131.34
21.81
141.12
138.59
122.50
129.54
21.93
138.50
137.01
126.31
129.52
20.85
141.60
139.51
126.70
129.94
21.71
138.89
135.32
128.81
129.95
21.94
2
3
4
s
R2
1
2
136.15
133.51
128.47
130.04
—
138.5
136.42
136.00
157.13
113.89
55.15
32.15
37.91
178
136.41
134.32
130.20
131.32
21.89
138.1
137.2
132.5
—
137.42
135.61
159.51
112.65
54.84
136.43
132.64
158.10
113.52
55.01
136.51
132.42
159.10
114.52
55.43
141.9
134.6
136.41
132.51
128.43
129.31
21.01
133.67
159.51
113.41
57.12
3
18.01
127.04
129.61
129.61
34.01
4
s
—
CH
CH2
COO
Sn-CH3
119Sn
21.52
40.45
182
30.01
39.45
178
34.51
39.46
31.98
40.16
29.71
40.43
178.62
21.86
132.61
29.91
36.9
27.53
37.98
31.48
43.14
32.14
37.95
38.51
178.5
22.52
131.00
178.56
22.45
132.63
178.43
22.45
130.99
178.5
22.23
132.92
178.5
22.01
131.90
177.69
22.21
125.81
178.0
22.00
132.91
22.20
131.45
22.14
133.64
22.10
133.35
aIn CDCl3 at 295 K.
bs ¼ Substituents on phenyl ring.
cChemical Shifts in ppm.
dR1 ¼ C6H5 (1–6), p-CH3C6H4 (7–11).
eR2 ¼ CH3 (1), C6H5 (2,10), o-CH3OC6H4(3,7), m-CH3OC6H4 (4,8), p-CH3C6H4 (5,11), p-ClC6H4 (6), p- CH3OC6H4 (9).
attached to the tin atom in all synthesized compounds. The these compounds is the presence of GeCH chiral center and
2
well-resolved coupling constant, J[119Sn 2 1H], falls in the CH2 is prochiral center, and three hydrogen atoms of the unit
range of 58–59.8 Hz and is indicative of tetrahedral geometry GeCHCH2 comprising of three hydrogen atoms that appear as
of the compounds in a non-coordinated solvent,[21,22] which is two sets of multiplets in the region of 3.15–3.82 ppm and
further supported by bond angle (111–1128) calculated by 2.41–2.81 ppm, respectively.[24]
using Lockhart’s equation.[23] Another characteristic feature of
13C NMR Spectroscopy
The 13C NMR spectral data of the synthesized compounds is
given in Table 4. The number of the signals found corresponds
with the presence of magnetically non-equivalent carbon
atoms, which were assigned by comparison with literature
values.[25,26] The carbon atom directly attached to tin
resolved in the expected region 21.86 to 22.54 ppm. The
aromatic carbon present in germanium-substituted ligand
acids were assigned by comparing the experimental chemical
shifts with those calculated form the incremental method.[27]
119Sn NMR data for these compounds, listed in Table 4,
show single resonance in the region 125.87–133.64 ppm
and this further supports the four coordination of tin in
solution.[28]
X-Ray Crystallography of (CH3)3Sn (C22H21O2Ge)
The crystal structure of (CH3)3Sn(C22H21O2Ge) is depicted
in Figure 2. The relevant structure refinement data, selected
FIG. 2. X-ray structure of: [Trimethyltin(IV)-3-(Triphenylgermyl)-3-methyl)
propionate].

170
M. K. KHOSA ET AL.
bond length and bond angles are given in Table 5 and Table 6.
In this compound, germanium adopts a distorted tetrahedral
geometry C-Ge-C, with its angles lying in the range of
107.34(13) and 113.98(13)8. The Ge(1)-C(3) distance,
1.976(3), is significantly longer than the Ge(1)-C(8), Ge(1)-
C(14) and Ge(1)-C(20) within 3 s limits with mean value of
TABLE 6
˚
Selected bond lengths [A] and bond angels [8] of compound (1)
Bond lengths
Bond angles
Sn(1)-C(5)
Sn(1)-C(6)
2.110(3)
2.115(3)
2.117(3)
˚
1.952(3)A. The geometry around tin atom is trigonal bipyramid
Sn(1)-C(7)
Sn(1)-O(1)
with the equatorial plane being defined by three methyl carbon
atoms with oxygen atoms occupying the axial positions. The
three Sn-C distances are equal within the experimental error
˚
[2.110(3), 2.115(3), 2.117(3) A]. The Sn-O bond lengths are
significantly different [Sn1-O1 2.155(2) and Sn1-O2 2.533(2)
2.155(2)
2.533(2)
Sn(1)-O(2)#1
Ge(1)-C(20)
Ge(1)-C(8)
1.948(3)
1.951(3)
Ge(1)-C(14)
Ge(1)-C(3)
1.957(3)
1.976(3)
˚
˚
A]. The shorter C1-O1 bond, 1.287 A, and the longer Sn1-
˚
O1 bond, 2.533(2) A, share the same oxygen atom. This
O(1)-C(1)
O(2)-C(1)
1.287(4)
1.226(3)
could be because one of the carboxyl oxygen atom is coordi-
nated to tin with a longer Sn-O distance because the C-O
bond keeps some of its double bond character. The central
methyl tin group bridges two neighboring germanium substi-
tuted carboxylic acid ligand via ester type O-C55O form
after organotin coordination to form a one-dimensional poly-
meric structure.[29]
C(5)-Sn(1)-C(6)
C(5)-Sn(1)-C(7)
C(6)-Sn(1)-C(7)
C(5)-Sn(1)-O(1)
C(6)-Sn(1)-O(1)
C(7)-Sn(1)-O(1)
C(20)-Ge(1)-C(8)
C(20)-Ge(1)-C(14)
C(8)-Ge(1)-C(14)
C(20)-Ge(1)-C(3)
C(8)-Ge(1)-C(3)
C(14)-Ge(1)-C(3)
114.77(15)
127.50(15)
115.02(14)
94.25(12)
92.82(11)
98.91(11)
107.34(13)
108.73(12)
108.41(12)
113.98(13)
110.27(12)
107.99(12)
BIOLOGICAL ACTIVITY
The antibacterial activity of synthesized compounds
containing germanium were screened against different types
of bacteria, E. coli, B. substilis, S. flexinari, S. auereus, P. aer-
uginosa and S. typhi. The results have been compared with the
Symmetry transformations used to generate equivalent atoms:
#1-x,y þ 1/2, -z þ 1/2, #2-x,y-1/2, -z þ 1/2.
TABLE 5
Crystal data and structure refinement of compound (1)
reference drug imipenum and are listed in Table 7. It is well
documented that the trimethyl complexes are more biocidally
active than the other class of alkyl species. All compounds
show good activity; compounds (6) was found to be more
active than the reference drug. The greater activity of this
compound is probably due to the presence of chlorine in the
ligand acid, which itself antibacterial.[30]
Empirical formula
Formula weight
Crystal system
Space group
C25H30GeO2Sn
553.77
Monoclinic
P21/c
13.901(3)
9.440(2)
˚
a(A)
˚
b(A)
˚
c(A)
19.017(5)
97.632(14)
The antifungal activity of the compounds was tested against
various fungi, T. longifusus, C. albicans, A. flavus, M. canis, F.
solani and C. glaberata. The results are summarized in Table 8.
The results showed that most of the compounds show sig-
nificant activity against all tested fungi except C. albicans.
The increased fungicidal activity of trimethyltin derivatives
is due to the triarylgermyl substituted ligand acid which
could act as carrier in this series.[31]
b(8)
Volume
3
˚
2473.4(10)A
Z
Absorption coefficient
4
2.242 mm21
27.5
10526
u
max(o)
Reflections collected
Independent reflections
Max. and min. transmission
Goodness-of-fit on F2
5632 [R(int) ¼ 0.029]
0.807 and 0.663
1.02
Brine Shrimp (Artemia Salina), a tiny crustacean, was used
for the determination of toxicity of compounds. The results are
given in Table 9. The LD50 values were found in between
5.01–501.00 mg/mL which suggests, comparatively, a high
degree of toxicity for these compounds except compounds I,
II and III which show lower toxicity with lethal dose greater
than 35 mg/mL.
Final R indices [I . 2sigma(I)]
R1 ¼ 0.032,
wR2 ¼ 0.068
R1 ¼ 0.053,
wR2 ¼ 0.077
0.55
R indices (all data)
23
˚
max(e.A
d
)

BIMETALLIC TRIMETHYLTIN(IV) GERMAPROPIONATE SYNTHESIS
171
TABLE 7
Antibacterial activity dataa–c of organotin derivatives of (1–10) containing germanium (in vitro)
Zone of inhibition of sample (mm)
Zone of inhibition of
std. drug (mm)
Name of bacteria
1
2
3
4
5
6
7
8
9
10
Escherichia coli
Bacillus subtilis
Shigella flexenari
Staphylococcus
Pseudomonas
29
10
—
42
10
30
10
—
40
10
25
10
8
28
10
10
35
8
14
10
12
14
8
28
30
30
40
23
10
—
—
—
6
29
—
10
—
—
26
10
—
—
9
15
10
8
30
31
33
43
25
8
8
7
5
aeruginosa
Salmonella typhi
40
39
36
40
14
39
15
32
39
12
41
aConcentration of sample ¼ 3 mg/mL.
bConcentration of standard drug (Imipenum) ¼ 10 mg/disc.
c(2) ¼ No activity.
TABLE 8
Antifungal activity dataa–c of organotin(IV) derivatives containing germanium (in vitro)
Zone of inhibition of sample
Std. drug MIC Zone of inhibition
Name of fungus
1
2
3
4
5
6
7
8
9
10
30
mg/mL
Miconazole
00
of std. drug
Trichophyton
longifusus
69
60
65
61
40
68
65
70
35
70
Candida albicans
Aspergillus flavus
99
86
—
98
—
60
—
40
—
109 109 105
—
65
—
30
—
110
20
—
—
—
Amphotericine
in B
Miconazole
Microsporum canis
Fusarium solani
Candida glaberata
88
30
84
30
93
44
40
85
51
35
95
25
20
95
92
69
88
20
98 102
92
35
25
20
20
20
72
98
73
00
00
30
106
105
110
aConcentration of sample ¼ 400 mg/mL of DMSO.
bIncubation temperature (period) ¼ 27 + 18C (7 days).
c( 2 ) ¼ No activity.
TABLE 9
Cytotoxicity dataa–c of organotin(IV) derivatives containing germanium
Comp. no.
1
2
3
4
5
6
7
5
9
10
6.00
Std. drug
7.46
LD50 (mg/mL)
61.00
59.98
501.00
60.00
35.86
05.01
05.91
16.90
16.90
aOrganism ¼ Artemia salina (brine shrimp) in vitro
bStandard drug ¼ Etoposide.
cLD50 ¼ Lethal dose at which 50% organisms die.
Supplementary Data
Number: 252060. Copies of the data can be obtained on request
Crystallographic data for the compound (I) have been depos- to CCDC,12 Union Road, Cambridge CB21 EZ, UK. E-mail:
ited with Cambridge Crystallographic Data Center as CCDC deposited@ccdc.cam.ac.uk or ,http// www.ccdc.cam.ac.uk..

172
M. K. KHOSA ET AL.
of Di- and triorganotin(IV) derivatives containing germanium:
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