Synthesis, structural characterization, Hirshfeld surface analysis and in vitro-antimicrobial activities of triphenyltin (IV) compounds of azo-carboxylates derived from 2- or 4-amino benzoic acids and naphthalen-1 or 2-ol

Article abstract of DOI:10.1016/j.molstruc.2020.128971

Synthesis of three new triphenyltin(IV) compounds 1–3 were reported by the reaction of azo-carboxylic acid ligands viz.2/4-(2-hydroxynaphthylazo)-benzoic acids [compounds 1 and 2] or 2-(4-hydroxynaphthylazo)-benzoic acid [compound 3] with triphenyltin(IV)

Full text of DOI:10.1016/j.molstruc.2020.128971

Journal Pre-proof
Synthesis, structural characterization, Hirshfeld surface analysis and
in vitro-antimicrobial activities of triphenyltin (IV) compounds of
azo-carboxylates derived from 2- or 4-amino benzoic acids and
naphthalen-1 or 2-ol
Paresh Debnath , Keisham Surjit Singh , Swatika Sharma ,
Pratima Debnath , S.Sureshkumar Singh , Les law Siero n´ ,
Waldemar Maniukiewicz
PII:
S0022-2860(20)31295-3
DOI:
Reference:
https://doi.org/10.1016/j.molstruc.2020.128971
MOLSTR 128971
To appear in:
Journal of Molecular Structure
Received date:
Revised date:
Accepted date:
16 May 2020
23 July 2020
24 July 2020
Please cite this article as: Paresh Debnath , Keisham Surjit Singh , Swatika Sharma ,
Pratima Debnath , S.Sureshkumar Singh , Les law Siero n´ , Waldemar Maniukiewicz , Synthesis,
structural characterization, Hirshfeld surface analysis and in vitro-antimicrobial activities of triphenyltin
(
2
IV) compounds of azo-carboxylates derived from 2- or 4-amino benzoic acids and naphthalen-1 or
-ol, Journal of Molecular Structure (2020), doi: https://doi.org/10.1016/j.molstruc.2020.128971
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Highlights






Three triphenyltin(IV) compounds 1-3 were synthesized and characterized.
1 showed intermediate between distorted TBP and square-pyramidal geometry.
3 exhibited distorted tetrahedral geometry with monomeric structure.
Hirshfield surfaces analysis of 1 and 3 observed different stacking interactions.
Compounds were isostructural and adopted four coordinated structure in solution.
Compounds showed significant antimicrobial activity.

Synthesis, structural characterization, Hirshfeld surface analysis and in vitro-
antimicrobial activities of triphenyltin (IV) compounds of azo-carboxylates
derived from 2- or 4-amino benzoic acids and naphthalen-1 or 2-ol
a
a,d*
b
a
Paresh Debnath , Keisham Surjit Singh , Swatika Sharma , Pratima Debnath , S.Sureshkumar
b
c
c*
Singh , Lesław Sieroń , Waldemar Maniukiewicz
a
Department of Chemistry, National Institute of Technology Agartala, Jirania, Tripura (west)-799046,
India
b
Department of Forestry, North Eastern Regional Institute of Science And Technology, Nirjuli, Arunachal
Pradesh -791109, India
c
Institute of General and Ecological Chemistry, Lodz University of Technology, 90-924 Lodz,
Zeromskiego 116, Poland
Department of Chemistry, Manipur University, Canchipur -795003, Imphal, Manipur, India
d
Abstract
Synthesis of three new triphenyltin (IV) compounds 1-3 were reported by the reaction of azo-
carboxylic acid ligands viz.2/4-(2-hydroxynaphthylazo)-benzoic acids [compounds 1 and 2] or 2-
(
4-hydroxynaphthylazo)-benzoic acid [compound 3] with triphenyltin(IV) hydroxide. The
compounds were completely characterized with the help of elemental analysis, IR and
1
13
119
multinuclear [ H, C and Sn]-NMR spectroscopy. The mode of coordination and geometry
around tin atoms in compounds 1 and 3 were determined by X-ray crystallography. Compounds
1
and 3 exhibited monomeric structure with intermediate deformation between the trigonal
bipyramidal and square-pyramidal geometry or distorted tetrahedral geometry around tin atom
respectively. Hirshfeld surface analysis for both structures was also performed. The main
1
19
difference between 1 and 3 is observed for stacking interactions. Sn NMR spectral study of all
the compounds suggested that the compounds adopted 4-coordinated tetrahedral structures in
solution. The antimicrobial activities of the compounds showed effective antibacterial activity
against S. aureus and antifungal activity against F. oxysporum. The antimicrobial activity of
these compounds was found to be higher than the tested standard compounds against some
selected microbes.
Key Words Triphenyltin(IV) complexes; crystal structures; Hirshfeld surfaces; NMR
spectroscopy; antimicrobial activities.
Corresponding authors:*E-mail address: surjitkeisham@yahoo.co.in, keishamchem@gmail.com
(
KSS), waldemar.maniukiewicz@p.lodz.pl (WM)

1
. Introduction
Chemistry of organotin (IV) carboxylates have been studied considerably for the last few
decades in organotin chemistry because of their interesting versatile molecular structures
exhibited as monomeric, dimeric, tetrameric, polymeric, hexagonal drum, ladder, macro-cyclic
and macro-cyclic porous structures [1-7]. Moreover, organotin (IV) carboxylates were also
investigated for the search of their possible biological applications. For instance they were found
to exhibit important biological properties such as anti-proliferation, antibacterial, cytotoxicity,
anti-tuberculosis and anticancer agents etc. [8-12] Similarly, attention have also been given to
organotin(IV) azo-compounds particularly organotin azo-carboxylates for their various possible
molecular architectures [13-18] and promising biological properties [15-18]. In recent years,
organotin compounds with some functionalized azo-carboxylate ligands derived from 2- and 4-
amino benzoic acids were studied extensively [19-22]. The antimicrobial and antidiabetic assays
for these compounds were performed and found to exhibit significant activity. In addition to this,
more recently we have also explored organotin (IV) compounds with some azo-carboxylate
ligands derived from 2- and 4-amino benzoic acids and naphthalen-2-ol [23, 24]. The molecular
structures of triorganotin (IV) compounds with these ligand systems were determined and
structure of all the complexes showed five coordinated distorted trigonal bipyramidal geometry
[
23]. Furthermore, the crystal structures of dibutyltin (IV) compounds with these ligand systems
were also determined and study of these structures revealed that the geometry around tin atoms
adopted five coordinated distorted trigonal bipyramidal to six coordinated distorted octahedral or
skew trapezoidal structures depending on the stoichiometric reaction ratios and type of the
ligands employed [24]. Similarly, molecular structures and antidiabetic properties of organotin
(
IV) complexes with a new series of azo-carboxylate derived from 2- amino benzoic acid and
naphthalen-1-ol were also studied [25]. The molecular structures of tributyltin and trimethyltin

(
IV) complexes with this azo-carboxylate ligand exhibited distorted trigonal bipyramidal
geometry while dibutyltin (IV) complex showed dinuclear structure with skew trapezoidal and
pentagonal bipyramidal geometry around the two tin atoms in the dinuclear structure
[
25].Therefore, in continuation with our previous work in this research area, now we report
herein three new triphenyltin (IV) compounds with these ligands i.e. azo-carboxylate ligands
prepared from diazo-coupling reaction of 2 or 4-amino benzoic acids and naphtalen-1-ol or
naphthalen-2-ol. In this present contribution, we have employed carboxylate ligands that have
variation in the position of carboxylate functionality in the diazo-part (2 or 4- positions) and also
varied the position of hydroxy group in the coupling moieties of the molecule (i.e. naphalen-1 or
2
-ol). By using carboxylate functionality at different positions in the diazo-part and introducing a
hydroxy group at different position in the coupling moieties, we would expect to afford
organotin (IV) compounds with different structures which would influence their biological
properties. Thus, considering all these facts, we have synthesized three new triphenyltin (IV)
compounds using these ligands and the synthesized compounds were completely characterized
1
13
119
by elemental analysis, IR and multinuclear ( H, C and
Sn)-NMR spectroscopy. The
structures of compounds 1 and 3 were determined and the results are discussed and reported
herein. In addition to this, Hirshfeld surface analysis for the structure of compounds 1 and 3 were
also performed. Finally, all the synthesized compounds were screened for their antimicrobial
activity and the results of the assay are discussed and compared with standard antibiotics.
2
2
2
. Experimental
.1 Materials and methods
-aminobenzoic acid, 4-aminobenzoic acid, 1-naphthol, 2-naphthol and triphenyltin(IV) chloride
were purchased from Merck and were used without further purification. Solvents were purified

3 3
and dried using standard procedure. Ph SnOH was synthesized from Ph SnCl using aqueous
solution of NaOH following the standard procedure [26]. Elemental analysis was performed on
Perkin Elmer 2400 series II instrument. Shimadzu FT-IR-8400S spectrophotometer in the range
-
1
of 4000-400 cm was employed for recording IR spectra with samples investigated using KBr
1
13
discs. The NMR ( H, C) spectra for the compounds were recorded on a Bruker AMX 400
1
19
spectrometer and were measured at 400.13 and 100.62 MHz respectively whereas Sn NMR
spectra of the compounds were recorded on ECZR Series 600 MHz NMR spectrometer and
1
13
measured at 223.75 MHz. H and C chemical shift was referenced to Me
4
Si set at 0.00 ppm
1
19
while Me
4
Sn was employed as reference for Sn chemical shifts and set at 0.00 ppm.
2
2
.2. Synthesis
1
2
.2.1. Synthesis of 2/4-(2-hydroxynaphthylazo) benzoic acid (H
2
L and H
2
L ) and 2-(4-
3
hydroxynaphthylazo) benzoic acid (H
2
L )
1
The azo carboxylate ligands viz. 2-(2-hydroxynaphthylazo) benzoic acid (H
2
L ), 4-(2-
2
3
hydroxynaphthylazo) benzoic acid (H
2
L ) and 2-(4-hydroxynaphthylazo) benzoic acid (H
2
L )
were prepared by simple diazo-coupling reaction of 2-aminobenzoic acid or 4-aminobenzoic
acid with naphthalen-1-ol or naphthalen-2-ol using our similar reported procedures [23, 25]. 2-
1
(
2-hydroxynaphthylazo)benzoic acid (H
2
L ): red colour; Yield: 8.1 g, 76 %; m. p.: 260-262 °C;
2
4
-(2-hydroxynaphthylazo)benzoic acid (H
2
L ): red colour; Yield: 8.5 g, 79 %; m. p.: 290-295
3
°
C; 2-(4-hydroxynaphthylazo)benzoic acid (H
2
L ): deep red colour ; Yield: 6.9 g, 65 %; m. p.:
1
-3
2
32-234°C. The structural formula and numbering scheme for the ligands H
2
L
are shown in
Scheme 1.
<Scheme 1>
1
2
3
.2.2. Synthesis of Ph SnHL (1)

Triphenyltin(IV) compound 1 was synthesised by the reaction of 2-(2-hydroxynaphthylazo)
benzoic acid with triphenyltin hydroxide in 1:1 (M: L) molar reaction ratio in anhydrous toluene
using Dean-Stark apparatus. In this synthetic procedure, 2-(2-hydroxynaphthylazo) benzoic acid
(
0.2385 g, 0.8167 mmol) was dissolved in 50 mL anhydrous toluene with continuous stirring to
yield a red coloured suspension. To that suspended solution, 0.3 g (0.8167 mmol) triphenyltin
hydroxide was added and clear red coloured solution appeared immediately. The reaction
mixture was then continued to refluxing for about 6 hours fitted with the Dean Stark apparatus.
The solution was then filtered and the filtrate was kept for evaporation at room temperature to
afford pure red crystals of the compound. Yield: 79 %; m. p.: 215-217 °C. Anal. found: C, 65.87;
-1
H, 4.19; N, 4.72%. Calc. for C35
H
26
N
2
O
3
Sn: C, 65.55; H, 4.09; N, 4.37%. IR (KBr, cm ): 3450
1
ν(N-H), 1619 ν(COO)asym, 1478 ν(N=N), 1155 ν(C-O), 697 ν(Sn-C), 470 ν(Sn-O). H NMR
(
CDCl
.4 Hz], 8.21 [d, 1H, H-6, J = 8.0 Hz], 8.03 [m, 1H, H-4], 7.88 [m, 1H, H-4′], 7.59 [m, 1H, H-6´
and H-8], 7.35 [t, 1H, H-5′, J = 7.6 Hz ], 7.16 [t, 1H, H-7, J = 7.6 Hz], 6.71[d, 1H, H-3, J = 9.6
3 H
, 400.13 MHz) δ , Ligand skeleton: 8.41 [d, 1H, H-9, J = 8.0 Hz], 8.27 [d, 1H, H-3′, J =
8
1
3
Hz]; Sn-Ph skeleton: 7.95 [m, 6H, H-o], 7.48 [m, 9H, H-m and H-p] ppm. C NMR (CDCl
00.62 MHz) δ , Ligand skeleton: 179.9 [COO], 172.9 [C-2],145.1 [C-1′], 141.9 [C-1], 134.45
C-4], 134.2 [C-5ʹ], 132.9 [C-4′], 131.4 [C-3ʹ], 129.4 [C-10], 128.8 [C-5], 128.7 [C-6], 127.7 [C-
3
,
1
C
[
8
1
], 126.8 [C-9], 123.9 [C-7], 122.7 [C-6′], 117.2 [C-3], 116.5 [C-2′]; Sn-Ph skeleton: 138.7 [C-i],
2
119/117
13
4
119/117
13
3
37.5 [C-o] J [
Sn- C (48.8 Hz)], 130.4 [C-p] J [
Sn- C (13.3 Hz)], 129.1 [C-m] J
119/117
13
119
[
Sn- C (64.7 Hz)] ppm. Sn NMR (CDCl3, 223.75 MHz): -104.7 ppm. The numbering
scheme for triphenyltin skeleton is shown below:

Sn
i
o
m
p
2
2
3
.2.3. Synthesis of Ph SnHL (2)
Compound 2 was synthesised following the analogous procedure as in case of compound 1 by
the reaction of 4-(2-hydroxynaphthylazo)benzoic acid instead of 2-(2-hydroxynaphthylazo)
benzoic acid with triphenyltin hydroxide in 1:1 (M: L) molar reaction ratio in anhydrous toluene
using Dean-Stark apparatus. The solid product obtained from filtrate was recrystallized from
anhydrous toluene to yield deep red crystalline product of compound 2. Yield: 69%; m. p.: 182-
1
4
26 2 3
84 °C. Anal. found: C, 65.37; H, 3.91; N, 4.18%. Calc. for C35H N O Sn: C, 65.55; H, 4.09; N,
-1
.37 %. IR (KBr, cm ): 3410 ν(N-H), 1619 ν(COO)asym, 1485 ν(N=N), 1165 ν(C-O), 671 ν(Sn-
1
C), 495 ν(Sn-O). H NMR (CDCl
3
, 400.13 MHz) δ
H
, Ligand skeleton: 8.46 [d, 1H, H-9, J = 8.0
Hz], 8.22 [d, 2H, H-3′, H-5′, J = 8.8 Hz], 7.90 [m, 1H, H-4], 7.76 [m, 1H, H-6], 7.65 [m, 3H, H-
2
′, H-6′ and H-8], 7.39 [t, 1H, H-7, J = 7.2 Hz], 6.74 [d, 1H, H-3, J = 9.6 Hz ]; Sn-Ph skeleton:
1
3
7
3 C
.82 [m, 6H, H-o], 7.49 [m, 9H, H-m and H-p] ppm. C NMR (CDCl , 100.62 MHz) δ , Ligand
skeleton: 177.7 [COO], 172.1 [C-2], 146.8 [C-1′], 142.2 [C-1], 133.6 [C-4], 132.6 [C-2′, C-6′],
1
1
31.1 [C-4′], 129.5 [C-10], 128.8 [C-5], 128.5 [C-8], 128.2 [C-9], 126.8 [C-7], 126.2 [C-6],
2
119/117
13
22.3 [C-3], 117.0 [C-3′ and C-5′]; Sn-Ph skeleton: 138.5 [C-i], 137.1 [C-o] J [
Sn- C (47.8
4
119/117
13
3
119/117
13
119
Hz)], 130.4 [C-p] J [
Sn- C (13.1 Hz)], 129.1 [C-m] J [
Sn- C (49.81 Hz)] ppm.
Sn
NMR (CDCl3, 223.75 MHz): - 109.8 ppm.

3
2
3
.2.4. Synthesis of Ph SnHL (3)
A similar synthetic procedure as described above as in case of compound 1 was followed for the
synthesis of compound 3 where 2-(4-hydroxynsaphthylazo)benzoic acid was used as azo-
carboxylate ligand instead of 2-(2-hydroxynaphthylazo) benzoic acid with triphenyltin (IV)
hydroxide in 1:1 (M:L) molar reaction ratio in anhydrous toluene using the Dean-Stark
apparatus. The compound was recrystallized from anhydrous toluene to get pure deep red
crystals of compound 3. Yield: 73 %; m. p.: 147-149 °C. Anal. found: C, 65.97; H, 4.79; N, 4.91
-1
%
. Calc. for C35
H
26
N
2
O
3
Sn: C, 65.55; H, 4.09; N, 4.37%. IR (KBr, cm ): 3435 ν(N-H), 1623
1
ν(COO)asym, 1475 ν(N=N), 1155 ν(C-O), 733 ν(Sn-C), 506 ν(Sn-O). H NMR (CDCl
3
, 400.13
MHz) δ
H-3, J = 7.6 Hz], 7.97 [m, 1H, H-2], 7.89 [m, 1H, H-7], 7.74 [m, 1H, H-8], 7.64 [t, 1H, H-4′, J ꢁ
.6 Hz], 7.54 [ꢂ, 1H, H-6 ], 7.02 [ꢃ, 1H, H-5´, J = 8.0 Hz], 6.62 [d, 1H, H-3, J = 10.4 Hz ]; Sn-
Ph skeleton: 7.81 [m, 6H, H-o], 7.51 [m, 9H, H-m and H-p] ppm. C NMR (DMSO-d
MHz) δ Ligand Skeleton: 185.2 [COO], 174.0 [C-4], 145.6 [C-1′], 135.9 [C-1], 135.0[C-5
33.9 [C-10], 132.1 [C-3ʹ], 132.3 [C-4ʹ], 130.4 [C-6], 113.5 [C-3]; other signals: 130.1, 128.2,
H
, Ligand skeleton: 12.59 [s, 1H, OH], 8.44 [d, 1H, H-9, J = 8.0 Hz], 8.18 [d, 2H, H-6,
ꢀ
7
ꢀ
1
3
6
, 100.62
],
C
ꢀ
1
1
2
119/117
13
26.2, 124.3, 123.1, 121.3, 114.4; Sn-Ph skeleton: 138.1 [C-i], 137.0 [C-o] J [
Sn- C (48
4
119/117
13
3
119/117
13
119
Hz)], 130.7 [C-p] J [
Sn- C (13.1 Hz)], 129.3 [C-m] J [
Sn- C (63.4 Hz)] ppm. Sn
NMR (CDCl3, 223.75 MHz): - 102.1 ppm.
2
.3. X-ray crystallography
Single crystal X-ray diffracꢃion daꢃa were collecꢃed by ꢃhe ω-scan technique using MoK
λ = 0.71073Å) radiation. Both crystals of compounds 1 and 3 were studied at 100(3) K using a
α
(
RIGAKU XtaLAB Synergy, Dualflex, Pilatus 300K diffractometer [27] with Photon Jet micro-
focus X-ray Source. Data collection, cell refinement, data reduction and absorption correction

were carried out using CrysAlis PRO software [27]. The crystal structures were solved by using
direct methods with the SHELXT 2018/2 program [28]. Atomic scattering factors were taken
from the International Tables for X-ray Crystallography. Positional parameters of non-H-atoms
2
were refined by a full-matrix least-squares method on F with anisotropic thermal parameters by
using the SHELXL 2018/3 program [29]. Hydrogen atoms participating in hydrogen bonding
were found on the Fourier map and freely refined while the other were placed in calculated
positions (C–H = 0.93–0.98 Å) and included as riding contributions with isotropic displacement
parameters set to 1.2-1.5 times the Ueq of the parent atom. Crystal data and structure refinement
parameters are shown in Table 1, while selected geometric parameters are collected in Table 2.
<
Table 1>
Table 2>
<
2
.4 Hirshfeld surfaces
The Hirshfeld surfaces (HS) [30] and the related 2D-fingerprint plots (FP) [31] were calculated
using Crystal Explorer software ver. 17.5 [32]. An in-depth introduction to HS analysis has been
described elsewhere [33]. The crystal data of 1 and 3 imported from CIF files were used for
analysis. Before starting the calculations the bond lengths to hydrogen atoms were set to
standardized neutron values (O–H= 0.983Å, N–H= 1.009Å and C–H= 1.083Å).
2
.5. Antimicrobial assay
Compounds 1-3 and ligands [H
1
-3
2
L ] were screened for their antimicrobial activity
following modified Kirby-Bauer-Disc-Diffusion Assay [34]. Antibacterial screening assays were
performed using three bacterial species (Escherichia coli, Pseudomonas aeruginosa and
Staphylococcus aureus). For anti-fungal screening, two fungi (Fusarium verticilloiodes and

Fusarium chlamydosporum) were used for compounds 1 and 2 while Fusarium oxysporum,
Candida albicans and Penicillium chrysogenum were employed for compound 3. Samples
solution were prepared by dissolving 1 mg of each sample in 20 μL DMSO and then solution
was diluted up to 1 mg/mL using sterile distilled water. Standard antibiotics solution (1mg/ mL
concentration) was also prepared as reference controls for both bacterial and fungal assays. Prior
to the antimicrobial assay, all the experimental organisms were revived by streaking on specific
agar media plates for fungi and in nutrient broth for bacteria. Bacterial inoculums were prepared
by inoculating 150 μL of fresh culture (24 hour old) after diluting up to 1:4 ratios in nutrient
broth. For preparing fungal inoculums, 150 μL of 7-days old fungal spore suspensions in sterile
water (diluted to 1/5) was added to the vials containing the fungal cultures and the colonies were
gently scraped out along with water and the suspension was vortexed at a minimum speed and
used directly as inoculums. Filter paper discs (Whatmann No.1) of 6 mm diameter were prepared
and sterilized by autoclaving prior to the assay. A thin layer of bacterial / fungal culture was
prepared using L-spreader on ꢃhe surface of Toꢂaꢃo Juice Agar, Plaꢃe Counꢃ Agar and King’s B
Agar media plates for bacteria; and Potato Dextrose Agar and Czapek Dox Agar media plates for
fungi. The plates were dried for about 1 minute inside the laminar air flow chamber. Three filter
paper discs previously saturated with test sample solutions (1mg/ mL) for screening and different
doses for quantitative assay were placed on the surface of the bacterial / fungal culture plates. A
standard antibiotic disc (conc. same as the test samples) of streptomycin / amphotericin B were
also prepared for comparison. The plates were incubated for 24 hours at 37º C for bacteria and
7
2 hours at 30º C for fungi inside BOD incubator. The bacterial and fungal inhibition zones
mm) were recorded for all samples as well as for the standard antibiotics. For quantitative dose
analysis, two bacterial species (S.aureus and P. aeruginosa) and two fungi (F. oxysporum and P.
(

chrysogenum) were employed. Concentrations of (25µg, 50µg, 100µg, 200µg, 500µg and
000µg) in 1 mL were used for bacteria for all the samples against the bacterial pathogens. For
1
fungal assay, the same concentration were also used for compounds 1 and 2 while for
compound 3 different concentration (250µg, 500µg, 750µg, 1000µg and 1500µg) in 1 mL were
tested. Inoculation procedure and incubation conditions were maintained same as described in
screening test.
3
. Results and discussion
3
.1. Synthesis
Triphenyltin(IV) compounds 1-3 were synthesized by reacting 2-(2-hydroxynaphthylazo)
1
2
benzoic acid [H
2
L ] (1) or 4-(2-hydroxynaphthylazo) benzoic acid [H
2
L ] (2) or 2-(4-
3
hydroxynaphthylazo) benzoic acid [H
2
L ] (3) with triphenyltin (IV) hydroxide in anhydrous
toluene using the Dean-Stark apparatus in 1:1 (M: L) molar reaction ratio. All the compounds
were obtained in good yield, stable at room temperature and they are soluble in most of the
common organic solvents. The reaction scheme for the synthesis of compounds 1-3 is shown in
Scheme 2.
<
Scheme 2>
3
3
.2. Spectroscopic characterization
.2.1. IR Spectroscopy
The IR spectroscopic data for the compounds were provided in experimental section while IR
spectroscopic data for the azo-carboxylate ligands were reported in our earlier report [23, 25].
1
-3
The azo-carboxylate ligands H
2
L
showed asymmetric [νasy(COO)] stretching absorption band
-1
at 1710, 1716 and 1673 cm respectively while in case of compounds 1-3, this IR stretching
-1
absorption bands was shifted to lower wave number in the range at 1619-1623 cm which is in

consistent for the carboxylate coordination to tin- atom in the complexes [15, 17, 23]. The IR
-
1
-1
absorption bands observed in the range 671-733 cm and 470-506 cm of compounds 1-3 could
be assigned for Sn-C and Sn-O respectively [19, 35, 36]. Moreover, broad IR absorption band
-
1
observed around 3400 cm in the compounds could be assigned for N-H stretching frequency
[
25].
1
13
119
3
.2.2. Multinuclear ( H, C and Sn) NMR spectroscopy
The synthesis and complete characterization data for the azo-carboxylate ligands used in this
1
13
119
present work has been described in our previous work [23, 25]. The H-, C- and Sn- NMR
spectra for the triphenyltin compounds 1-3 were recorded in CDCl and their spectroscopic data
3
were assigned subsequently by comparing with the spectroscopic data of the corresponding azo-
carboxylate ligands because of their data similarities. In proton NMR spectra of the compounds,
the aromatic protons were observed in the range 6.67-8.37 ppm while triphenyltin protons in the
1
3
compounds showed two multiplet peaks at 7.48-7.51 and 7.81-7.95 ppm. In C NMR spectra of
the compounds, the carbon signals for aromatic carbons appeared in the range 116.5-174.1 ppm
1
3
13
while C signals for (COO) were observed at around 177.7-185.2 ppm. Further, four C-
signals appeared in the range 129-139 ppm were assigned for the phenyl carbons; C-ispo (138.1-
1
38.7), C-ortho (137.0-137.5), C-para (130.4-130.7) and C-meta (129.1-129.3) ppm respectively
[
18, 19, 37]. Moreover, the coordination behaviour around tin atoms in solution state can be
n
119/117
13
n
investigated using J [
Sn- C] coupling constants and the corresponding observed
Sn- C] values for the triphenyltin (IV) compounds 1-3 were found to be in consistent
with those compounds with 4-coordinated quasi-tetrahedral geometry reported in the literature
J
1
19/117
13
[
1
19
[
14, 18, 19, 37, 38]. Furthermore, Sn -NMR spectroscopy study also used for confirming the
1
19
geometry around tin atom in the complexes in solution state. Sn chemical shift values for

compounds 1- 3 were observed at -104.78, -109.88 and -102.12 ppm respectively indicating all
the compounds adopted 4-coordinated tetrahedral structures in solution state [14, 18,19, 37-39].
Hence, it can be suggested that the 5-coordinated solid state structure of compound 1 is
dissociated into four coordinated structure while the solid state structure of compound 3 is also
retained in solution state (vide infra X-ray crystal structure).
3
.3. Description of the crystal structures
The atomic numbering scheme and the coordination around the tin atom for the complexes 1 and
are illustrated in Figs. 1 and 2, respectively. Selected bond lengths and bond angles are listed in
3
Table 2. In both structures 1 and 3, the ligands occur in the hydrazone form. The complex
1
Ph
3
SnHL (1) comprises discrete molecular units wherein the central Sn atom is five-coordinated
to the three phenyl ligands and the chelated by carboxylate group. The almost equal Sn–C bond
lengths [mean bond length Sn–C = 2.1263(18)Å] are consistent with those reported in the
literature [40]. The C–Sn–C bond angles [C(18)–Sn(1)–C(24), C(18)–Sn(1)–C(30), C(24)–
Sn(1)–C(30)] are 110.30(7)°, 108.94(7)° and 116.14(7)°, respectively and their sum of
3
35.41(7)° clearly differs from 360°. As is often seen in such complexes [41] the carboxylate is
unsymmetrically bidentate. The two oxygen atoms are bonded to Sn atom with significantly
different Sn–O distances of 2.0751(14)Å and 2.6472(12)Å respectively, according to the stronger
coordinative ability of the carboxylate O atom than the carbonyl O atom. Longer weak Sn(1)–
O(2) bond is considerably shorter than the sum of the van der Waals radii of the Sn and O atoms
(
3.68Å) [42] and should rather be considered as semi-coordinative but still of physical
significance. The Sn coordination sphere deformation can be explained by the Berry pseudo-
rotation mechanism [43] and characterized quantitatively by parameter τ defined by Addison et
al. [44], (τ = 0.58; cf. ꢃhe τ values for ꢃhe idealized geometries are τ = 0, square planar, τ = 1,

trigonal bipyramidal). The parameter τ indicates intermediate deformation between the trigonal
bipyramidal and square-pyramidal geometry. The intramolecular N-H…O hydrogen bonds
[
N(1)–H(1)…O(2) and N(1)–H(1)…O(3)] help to establish near planar conformation of
molecule (Table 2). Packing diagram of complex 1 is shown in Fig. S4. No other significant
supramolecular interactions were found.
<
Figure 1>
Like in structure 1, the structure of 3 is also built from monomeric molecules, but the Sn atom
has a distorted tetrahedral coordination geometry (Fig. 2). The coordination sphere involves the
3
three phenyl ligands and the carboxylate O-atom of the HL ligand. The range of the tetrahedral
angles at the Sn atom is 97.50(6)° to 122.19(6)°. The C–Sn–C angles are larger than the ideal
tetrahedral value, probably due to the steric effects arising between the phenyl ligands. The
carbonyl O(2) atom, interacts only weakly with the Sn-atom at a distance of 2.843(2)Å This
interaction is the cause of the distortion of the tetrahedral primary coordination sphere, but the
Sn(1)…O(2) distance is considered to be too long for the Sn atom to be described as truly five-
coordinate. Similar distorted tetrahedral geometry around the Sn atom was observed in
triphenyltin(IV) complex with 2-hydroxybenzoic acid derivative [45]. Due to the different
location of the hydroxy group in ligand, only one intramolecular hydrogen bond of type N-H…O
(
Table 3) is observed in 3. In addition the carbonyl O(2) atom also plays a role in stabilizing
structure through interaction of type C-H…O (Table 3, Fig. S5).
<
Table 3>
<
Figure 2>

3
.4. Hirshfeld surfaces analysis
1
3
2 2
The ligands H L and H L used for the synthesis of complexes differed in the position of the
hydroxy group in the molecule. The impact of this difference on intermolecular interactions
seemed interesting to analyze. For this reason the Hirshfeld surfaces (HS) and their associated
two-dimensional fingerprint plots (FP) were used to quantify intermolecular interactions. The 3D
Hirshfeld surfaces of the title compounds are illustrated in Figure 3, with maps dnorm and shape
index. The red spots on dnorm correspond to the dominant intermolecular interactions in the
crystals. The contributions of specific types of contacts to the Hirshfeld surfaces for compounds
1
and 3 have been summarized in Table 4 and Figure S6. Both, in structure 1 and 3 van der
Waals forces (H⋯H and C⋯H/H⋯C contacts) constitute the majority of forces contributing to
the stacking of the molecules in the structures. In structure 1 due to the involvement of two
oxygen atoms in intramolecular hydrogen bonds higher contribution of C···C contacts of 9.0 %,
than H···O/O···H contacts of 7.1% is observed. The reverse situation is seen in structure 3
where C···C and H···O/O···H contacts are 5.0 % and 7.1% respectively. This difference shows
the greater importance of stacking interactions in crystal packing of 1 than in 3.
<
Figure 3>
3
.5. Antimicrobial activity studies
The antimicrobial activity of all the synthesized compounds 1-3, tin starting material Ph
and the ligands were evaluated by screening against three bacterial and five fugal species. The
results of the antimicrobial screening test of the compounds, Ph SnOH and the ligands along
3
SnOH
3
with the standard compounds streptomycin for anti-bacterial test and amphotericin B / ampicillin
for antifungal test as reference controls are listed in Table 5. Quantitative dose analysis for
compounds 1-3 and standard compounds were also studied against two bacteria (S. aureus and P.

aeruginosa) and two fungi (F. oxysporum and P. chrysogenum). The results of the quantitative
assay of the compounds along with standard compounds are listed in Table 6. From dose
quantitative study, it is seen that, in general the antibacterial activity of compounds 1-3 and
standard compound streptomycin increases with increase in concentration (from 25 to 1000
μg/ꢂL) of the tested compounds. They showed maximum activity at 500 or 1000 μg/ꢂL againsꢃ
S. aureus. Compound 3 was found to be the most effective antibacterial agent at 1000 μg/ꢂL
(
17.7 mm) and exhibited activity higher than streptomycin (11.6 mm) at the same concentration
against S.aureus. The tin starting material Ph SnOH exhibited lower antibacterial activity as
3
compared to the compounds at higher concentration but did not show activity at lower
concentration against S. aureus. Compounds 1 and 3 showed higher antibacterial activity than
standard compound streptomycin against S.aureus. However, all the tested compounds did not
show any antibacterial activity at different dose against P. aeruginosa. Furthermore, antifungal
dose quantitative assay against F. oxysporum showed that the antifungal activity of the
compounds generally increases with increase in concentration up to certain optimum
concentration, and then activity decreases with increase in concentration (Table 6). Compounds
1
and 2 showed higher antifungal activity than compound 3 and the standard compound
amphotericin B against F. oxysporum. However, compounds 1 and 2 did not show any
antifungal activity against P. chrysogenum but compound 3, the tin starting material and
amphotericin B were found to exhibit antifungal activity against this fungus. The antimicrobial
activity of these compounds may be explained on the basis of the formation of hydrogen bonding
through hydroxy group with the active center of the cell constituents which consequently
interfere with the normal cell processes [46]. Furthermore, the antimicrobial activity of
triphenyltin (IV) compounds can be attributed to the presence of bulky phenyl groups which can

facilitate ꢃhe binding ꢃo biological ꢂolecules ꢃhrough π-π inꢃeracꢃions [13]. The results of the
antimicrobial activity study of all the screened microbes for the present triphenyltin (IV)
compounds could not be compared with those of the similar type of triphenyltin (IV)
compounds with azo-carboxylates reported earlier because of the different methodologies and
strains employed [47]. However, the antimicrobial activity of the present triphenyltin (IV)
compounds against the tested bacteria, S. aureus and fungus, F. oxysporum were comparable
with the reported tributyltin (IV) compounds of the similar ligands [23]. Few compounds were
also found to exhibit activities higher than the standard antibiotics, streptomycin and
amphotericin against few selected tested microbes.
4
. Conclusions
Three triphenyltin(IV) complexes 1-3 were synthesized by reacting three azo-carboxylic acid
ligands viz.2/4-(2-hydroxynaphthylazo)benzoic acids or 2-(4-hydroxynaphthyl azo)benzoic acid
with triphenyltin(IV) hydroxide. The compounds were characterized by elemental analysis, IR
and multinuclear NMR spectroscopy. The molecular structure of 1 and 3 was determined by X-
ray crystal structure analysis. In complex 1, the coordination sphere of Sn atom showed
intermediate deformation between the trigonal bipyramidal and square-pyramidal geometry,
while in 3 distorted tetrahedral geometry around tin atom is observed. Intra-molecular hydrogen
bonding between N-H...O were also present in both the structures. Hirshfeld surfaces analysis
was performed for the structure of compounds 1 and 3. The main difference between 1 and 3 is
observed for stacking interactions. NMR spectral study indicated that all the compounds adopted
four coordinated tetrahedral structures in solution. Thus five coordinated solid state structure of
compound 1 is suggested to dissociate into four coordinated structure while solid state structure

for compound
3
is also retained in solution. All tested compounds showed effective
antibacterial activity against S. aureus and significant antifungal activity against fungi F.
oxysporum. Compounds 1 and 3 showed higher antibacterial activity than standard compound
streptomycin against S. aureus while compounds 1 and 2 were found to display higher antifungal
activity than the standard antibiotic amphotericin B against F. oxysporum. Since the
antimicrobial activity of few compounds of the present series showed higher activity than the
tested standard compounds against few microbes, these compounds could be further studied to
enhance antimicrobial therapeutic properties.
Acknowledgements
Authors would like to thank IISc, Bangalore for NMR spectra and DBT, Govt. of India (Grant
No. BT/32/NE/2011) for Biotech Hub, Department of Forestry.
Supplementary materials
CCDC No. 2002480 and 2002481 contain the supplementary crystallographic data for
compounds 1 and 3 receptively. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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O
3
HO
O
HO
N
8
5'
2'
4
5
4
'
9
6'
2
7
6
OH
2
'
N
10
1
N
3'
1
3'
6
7
1'
1
'
10
N
5
4'
6'
9
4
2
8
OH
5'
3
1
2
2
-(2-hydroxynaphthylazo) benzoic acid (H L )
4-(2-hydroxynaphthylazo) benzoic acid (H L )
2
2
3
HO
O
OH
4
2
1
2'
5
N
3'
6
N
10
1'
4'
6'
9
7
5'
8
3
2
-(4-hydroxynaphthylazo) benzoic acid (H L )
2
1
2
Scheme 1. The structural formula and numbering scheme for the azo-carboxylate ligands H L ,
2
3
H
2
L and H
2
L .
HO
3
Ph
HO
3
Ph
Ph
O
4
5
Sn
4
5
O
2
1
2
1
HO
2'
O
2'
N
N
3'
3
'
6
7
6
7
Ph SnOH
N
N
3
1
'
10
1'
6'
10
1
: 1 (M : L)
4'
6'
9
4
'
9
Toluene
Reflux for 6-7 hours
5'
8
5'
8
1
1
H L : 2'-COOH, 2-OH
Ph SnHL (1)
2
3
2
2
H L : 4'-COOH, 2-OH
Ph3SnHL (2)
2
3
3
Ph SnHL (3)
H L : 2'-COOH, 4-OH
3
2
Scheme 2. Reaction scheme for the synthesis of triphenyltin (IV) compounds 1- 3.

Table 1. Crystal data and structure refinement parameters for compounds 1 and 3.
Parameters
Empirical formula
Formula weight
Temperature (K)
Wavelength ( Å)
Crystal system
Space group
a (Å)
1
3
C
35
H
26
N
2
3
O Sn
C
35 26 2 3
H N O Sn
641.29
100(3)
0.71073
monoclinic
P2 /c
16.1609(2)
10.2454(1)
18.1466(2)
90
641.29
100(3)
0.71073
triclinic
P-1
11.1879(1)
11.5828(1)
11.9869(1)
103.979(1)
1
b (Å)
c (Å)
α (º)
β (º)
γ(º)
113.908(1)
90
2746.82(6)
100.590(1)
103.737(1)
1415.51(3)
3
Volume (Å )
Z
4
2
3
1.551
1.505
Density (Mg/m )
-
1
0.971
1296
0.35 x 0.60 x 0.65
2.8, 25.0
0.942
648
0.16 x 0.19 x 0.60
2.9, 25.0
Absorp. coeff. ( mm )
F(000)
Crystal size (mm )
3
Theta range for data collection
Index ranges
-19<=h<=19; -12<=k<=12; -13<=h<=13; -13<=k<=13
-
21<=l<=21
-14<=l<=14
38945
Reflection collected
147481
Independent reflections
Goodness of fit on F
4851 [R(int) = 0.033]
1.13
5010 [R(int) = 0.027]
1.05
2
Final R indices [I>2sigma (I)]
R indices (all data)
0.0177
0.0179
0.0152
0.0156
-
3
0.34 and -0.28
0.32 and -0.25
Largest diff. peak and hole (eÅ )

Table 2 Selected bond lengths (Å) and bond angles (º) for compounds 1 and 3.
Atoms
1
3
Bond Length (Å)
Bond Length (Å)
Sn(1)-O(1)
Sn(1)-O(2)
Sn(1)-C(18)
Sn(1)-C(24)
Sn(1)-C(30)
Atoms
2.0751(14)
2.6472(12)
2.1317(17)
2.1224(18)
2.1248(19)
2.0555(11)
-
2.1213(16)
2.1203(16)
2.1212(15)
1
3
Bond Angle (º)
Bond Angle (º)
O(1)-Sn(1)-O(2)
O(1)-Sn(1)-C(18)
O(1)-Sn(1)-C(24)
O(1)-Sn(1)-C(30)
O(2)-Sn(1)-C(18)
O(2)-Sn(1)-C(24)
O(2)-Sn(1)-C(30)
54.08(5)
97.03(6)
110.57(6)
112.19(6)
151.05(6)
82.16(5)
86.77(6)
-
95.72(5)
108.37(5)
105.21(5)
-
-
-
C(18)-Sn(1)-C(24)
C(18)-Sn(1)-C(30)
C(24)-Sn(1)-C(30)
110.30(7)
108.94(7
116.14(7)
109.59(6)
112.24(6)
122.19(6)
Table 3 Hydrogen bonding parameters for compounds 1 and 3
Compound
D–H…A
d(D–H)
0.85(2)
0.85(2)
0.82(2)
0.95
d(H…A)
2.07(2)
1.96(2)
1.98(2)
2.59
d(D…A)
2.692(2)
2.616(2)
<(DHA)
129(2)
133(2)
N(1)-H(1)…O(2)
N(1)-H(1)…O(3)
N(1)-H(1)…O(2)
C(28)-H(28)…O(2)
1
3
2.6586(18) 140(2)
3.450(2) 151
#
1
Symmetry code: (#1) 1-x,-y,1-z

Table 4 Summary of the various contact contributions (in %) in Hirshfeld surface area for all
analyzed structures.
Contact type /Structure
1
49.8
30.2
7.1
9.0
-
3
…
H H
46.6
35.3
9.3
5.0
1.5
1.4
0.4
-
…
…
C H/H C
…
…
O H/H O
…
C C
…
…
N C/C N
…
…
N H/H N
2.4
0.8
0.6
-
…
…
O C/C O
…
N N
O…N/N…O
0.5

Table5. Antimicrobial screening test for azo-carboxylate ligands and compounds (zone of
inhibition in mm)
Ligands/
Bacteria
Fungi
Compounds
E.
S.
P.
F.
F.
F.
C.
P.
coli aureus aeroginosa verticiliodes chlamydosporium
oxysporum ablicans chrysogenum
1
H
H
H
1
2
3
2
2
2
L
L
L
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
2
3
-
18.6
12.7
*
*
*
-
-
-
15.5
15.2
23.0
22.0
11.0
*
8.7
13.7
*
*
*
*
*
*
*
*
*
14.0
15.0
10.3
*
5.0
2.0
*
-
-
*
12.3
4.6
*
Ph
3
SnOH
Streptomycin
Amphotericin-B
Ampicilin
10.5
*
*
*
4.0
12.6
5.3
*
*
*
-
-
*
*
*
(
-) = Not active; (*) = Not tested

Table 6. Results of quantitative assay for the compounds and standard antibiotics against
bacteria and fungi (in mm)
Compounds/standard Dose conc.
Bacteria
Dose conc.
for fungi
(in µg/mL)
Fungi
P. chrysogenum
antibiotics
for bacteria
in µg/mL)
S. aureus
P.
F.
(
aeroginosa
oxysporum
2
5
5
0
6.9
7.7
8.2
12.6
11.0
12.7
4.4
4.6
7.1
8.6
9.8
9.5
4.3
5.7
6.6
12.3
16.5
17.7
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
25
50
5.6
12.3
11.8
17.5
20.2
17.4
-
7.6
10.4
15.6
18.1
18.2
2.4
4.3
5.0
4.9
4.7
2.4
-
-
-
-
-
-
-
-
-
-
-
-
-
-
2.5
3.6
4.2
5.3
7.0
-
1
00
200
00
000
100
200
500
1000
25
1
2
3
5
1
2
5
5
0
50
1
00
200
00
000
100
200
500
1000
-
250
500
750
1000
1500
-
5
1
2
5
5
0
1
00
200
00
000
5
1
-
-
2
5
5
0
-
-
-
-
-
-
-
-
-
-
3.5
3.6
9.3
6.3
*
*
*
*
*
*
250
500
750
1000
1500
-
-
-
5.3
-
*
*
*
*
*
*
-
-
-
-
-
8.0
7.6
7.1
7.9
10.6
*
*
*
*
*
*
-
4.1
7.2
6.2
5.9
1
00
200
00
000
Ph
3
SnOH
5
4.0
7.9
4.2
5.2
8.6
9.5
10.0
11.6
*
*
*
*
*
1
2
5
5
0
-
250
500
750
1000
1500
1
00
200
00
000
Streptomycin
5
1
2
5
5
0
-
250
500
750
1000
1500
100
200
Amphotericin-B
500
1000
*
5
.7
6
.0
(-) = Not active; (*) = Not tested

Fig. 1 The molecular structure of 1. Displacement ellipsoids drawn at 50% probability level.
Fig 2. The molecular structure of 3. Displacement ellipsoids drawn at 50% probability level

a)
Compound 1
b)
Compound 3
Fig. 3 Hirshfeld surfaces, shape-index surface and fingerprint plot of compounds 1 (a), and 3 (b)
that are mapped with dnorm (left column), shape-index (middle column) and full fingerprint plot
(
right column).