Synthesis, characterization and biological evaluation of a nanorod five-coordinated Sn(IV) complex. Theoretical studies of (CH3)2Sn(O2PPh2)2

Article abstract of DOI:10.1002/aoc.4610

A new five-coordinated diorganotin(IV) complex with formula Sn(CH₃)₂Cl₂L (L?=?(C₆H₅)₂(O)P(NHC₆H₁₁)), with a rod-shaped nanostructure, was synthesized using a sonochemi

Full text of DOI:10.1002/aoc.4610

Received: 24 July 2018
DOI: 10.1002/aoc.4610
Revised: 20 August 2018
Accepted: 3 September 2018
F U L L P A P E R
Synthesis, characterization and biological evaluation of a
nanorod five‐coordinated Sn(IV) complex. Theoretical
studies of (CH3)2Sn(O2PPh2)2
Niloufar Dorosti1
| Hadis Mohammadpour2
1 Department of Chemistry, Lorestan
A new five‐coordinated diorganotin(IV) complex with formula Sn(CH3)2Cl2L
(L = (C6H5)2(O)P(NHC6H11)), with a rod‐shaped nanostructure, was synthe-
sized using a sonochemical method. The nanostructure was characterized
using various techniques. The bulk complex was also produced using a reflux
method applied to a solution of the reagents. The ligand and bulk form were
University, 68135‐465 Khorramabad, Iran
2 Department of Chemistry, Payame Noor
University, PO Box 19395‐3697 Tehran,
Iran
Correspondence
characterized using H NMR, 13C NMR, 31P NMR, 119Sn NMR, UV–visible
1
Niloufar Dorosti, Department of
Chemistry, Lorestan University, 68135‐
465, Khorramabad, Iran.
and infrared spectroscopies. By direct calcination of the synthesized complex
at 650°C, nanopowders were obtained with spherical‐like structure and diam-
eters of 40–100 nm (for bulk form) and 20–60 nm (for nanometric form).
Two different forms of Sn(IV) complex (C1, C2) and the corresponding ligand
were evaluated regarding their anticancer activity, as well as their influence
on both Gram‐positive and Gram‐negative classes of bacteria. Among the com-
pounds, nanostructured C2 was found to be the most active with IC50 of
62 0.03 and 92 0.09 μM against A2780 and PC‐3 cell lines. Preliminary
antibacterial experiments were carried out using the cup test method, in which
nanocomplex C2 showed better activity against all the selected bacteria than
other compounds. Moreover, single crystals of C3 were obtained by the interac-
tion of (CH3)2Cl2Sn with L in ethanol–water solution, where the Sn(IV) ion is
six‐coordinated with one‐dimensional polymeric chains. The intermolecular
interactions which connected the chains into a two‐dimensional framework
were supported by Hirshfeld surface analysis and fingerprint plots.
Email: nilufardorosti@gmail.com
KEYWORDS
anticancer, crystal structure, diorganotin, Hirshfeld, nanorod
1 | INTRODUCTION
complexes of various ligands such as carboxylates,[3]
thiolates[4] and dithiocarbamate derivatives[5] have been
Over the past few years, organotin compounds have
played a considerable role in organometallic chemistry
owing to various applications in diverse fields such as bio-
logical, agricultural, catalytic and industrial.[1] There are
several recent reports describing the effects of tin‐based
antitumour compounds against a large variety of human
cancer cell lines.[2] The anticancer activities of Sn(IV)
shown against certain types of cancer, mostly stronger
than cisplatin. Besides promising anticancer effects,
anti‐inflammatory, antiviral and antimicrobial activities
have been reported for a variety of organotins.[6] Though
a number of interesting Sn(IV) targets have been investi-
gated, the biological utility of such agents continues to be
questioned. Structural studies have also been prominent
Appl Organometal Chem. 2018;e4610.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4610

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DOROSTI AND MOHAMMADPOUR
in organotin chemistry. More recently, organotin com-
plexes with phosphoramide ligands have found consider-
able importance due to their coordination chemistry. It
should be noted most of these complexes are six‐coordi-
nated[7] and a few are five‐coordinated.[8]
ligand towards human ovarian cancer cell line (A2780)
and human prostate cancer cell line (PC‐3) was evaluated
using MTT assay. Antibacterial activity against three
Gram‐positive bacteria (Bacillus subtilis, Bacillus cereus
and Staphylococcus aureus) and two Gram‐negative bacte-
ria (Escherichia coli and Pseudomonas aeruginosa) was also
examined. Density functional theory (DFT) calculations
were performed to obtain related electronic and structural
properties of the complex to find probable structure–activ-
ity relationships. The crystal structure of C3, which was
obtained by reaction of L with Sn(CH3)2Cl2 from an etha-
nol–water solution using the branched tube method, was
established using X‐ray analysis. Quantum theory of atoms
in molecules (QTAIM) and natural bond orbital (NBO)
analyses were performed to obtain more information about
the electronic characteristics of C3 and nature of bonding
in the Sn–ligand interaction. Subsequently, an investiga-
tion of close intermolecular interactions in C3 via Hirshfeld
surface analysis was conducted.
It is well known that biological agents based on
chemicals have been effective for therapy; however, they
have been limited to use for medical devices due to toxicity
and multidrug resistance.[9] The biological activity of many
of compounds is markedly correlated with their structure,
size and morphology.[10] Reducing the particle size of mate-
rials is an efficient and reliable tool for improving their bio-
compatibility.[11] Nanometre‐scaled materials often exhibit
new interesting size‐dependent physical, chemical and bio-
logical properties that cannot be observed in their bulk ana-
logues. Despite considerable effort directed to the synthesis
of tin–phosphoramide complexes, little attention has been
focused to date on nanostructures of these complexes.[12]
Here, we report synthesis and characterization of a
phosphonic amide ligand with formula (C6H5)2(O)
P(NHC6H11) (L) for the production of a Sn(IV) complex
with the aim of finding more efficient biological activities.
Reaction of L with Sn(CH3)2Cl2 provided a five‐coordi-
nated complex, (CH3)2Cl2SnL, at two different sizes using
slow evaporation (C1) and sonochemical (C2) methods
(Scheme 1). In vitro cytotoxicity of the tin complexes and
2 | EXPERIMENTAL
2.1 | Instrumentation
All the chemicals used were commercially available and
were used as received without further purification. 1H
SCHEME 1 Formation of complex in bulk form C1 and nanoscale C2, and the nanopowders obtained from their calcination at 650°C.

DOROSTI AND MOHAMMADPOUR
3 of 14
NMR, 13C NMR, 31P NMR and 119Sn NMR spectra were
recorded with a Bruker Avance DRS 300 spectrometer at
96‐well plate and then incubated for 24 h at 37°C in 5%
CO2. An equal volume of additional medium containing
either the serial dilutions of the tested compounds, posi-
tive control (doxorubicin) or dimethylsulfoxide (DMSO)
as negative control was added to the desired final concen-
trations. The microtiter plates were further incubated for
24 and 48 h after adding all samples for determining cell
viability. MTT was added (20 μl of 5 mg ml−1 MTT in
phosphate‐buffered saline), and the plates were incubated
at 37°C for an additional 3–4 h. DMSO was then added to
dissolve the resultant crystals, and the optical absorbance
was measured at 570 nm with an Elisa reader. The results
were compared with those of a control reference plate
fixed on the treatment day, and the growth inhibition
was calculated for each drug contact period. Each assay
was set up in triplicate wells and repeated one to three
times. The IC50 value is defined as a sample concentra-
tion that inhibits 50% of cell growth and the values are
presented in Table 1. Also, to study the degree of selectiv-
ity in the cytotoxic activity of the compounds, separation
of lymphocyte was conducted according to the following
procedure.[14] Defibrinated or anticoagulant‐treated blood
was diluted with an equal volume of phosphate‐buffered
saline and layered carefully over Ficoll‐Paque PLUS
(without intermixing) in a centrifuge tube. After a short
centrifugation at room temperature (typically at 400 gav
for 30–40 min), lymphocytes, together with monocytes
and platelets, were harvested from the interface between
the Ficoll‐Paque PLUS and sample layers. This material
was then centrifuged twice in a balanced salt solution to
wash the lymphocytes and to remove the platelets.
1
300.13, 75.48, 121.49 and 111.86 MHz, respectively. H
and 13C chemical shifts were determined relative to internal
Me4Si. 31P and 119Sn chemical shifts were measured relative
to 85% H3PO4 and Sn(CH3)4 as external standards. Fourier
transform infrared (FT‐IR) spectra were obtained with a
Bruker model tensor 27 FT‐IR instrument with samples as
KBr pellets. Elemental analysis was performed using a
Heraeus CHN‐O‐RAPID apparatus. Melting points were
measured with an Electrothermal 9100 apparatus. Elec-
tronic spectra were recorded with a Varian Cary 100 UV–
visible spectrophotometer in the range 200–800 nm. An
ultrasonic bath (Rocker model Soner203H; 53 kHz and
220 V) was used for the ultrasonic irradiation. Nanoparti-
cles were characterized with a Hitachi S‐4160 scanning
electron microscopy (SEM) instrument. Energy‐dispersive
X‐ray spectroscopy (EDS) was performed using a MIRA5‐
LMU FE‐SEM instrument equipped with a Thermo EDAX
attachment. The morphology of the nanoparticles was
analysed using the images obtained with a Zeiss EM10C
100 kV transmission electron microscope. The X‐ray dif-
fraction pattern of dry nanoparticle powder was obtained
using an X'Pert Pro diffractometer (PANalytical) with
monochromatized Cu Kα radiation (λ = 1.54 Å). The ther-
mal behaviour was measured with a Perkin LMERS2 appa-
ratus between 20 and 800°C in a static nitrogen atmosphere.
2.2 | Anticancer Assay
The cytotoxic activities of ligand L and complex in bulk
form (C1) and nanosize form (C2) were determined with
two human cancer cell lines, namely A2780 (human
ovarian cancer cell line) and PC‐3 (human prostate can-
cer cell line), using MTT assay with doxorubicin as a con-
ventional anticancer agent. Briefly, cell lines suspended
in RPMI‐1640 containing 10% foetal bovine serum were
seeded at a density of 2 × 103–5 × 103 cells per well in a
2.3 | Antibacterial Evaluation
The cup‐plate agar method[15] was used to determine the
antibacterial activity of the synthesized compounds
against three Gram‐positive bacteria, namely B. cereus
(ATCC 11778), B. subtilis (ATCC 12711) and S. aureus
TABLE 1 Cytotoxicity activity of compounds against A2780 and PC‐3 cell cultures
IC50 SD (μM)
Compound
A2780
93 0.05
PC‐3
125 0.11
Ref.
(C6H5)2P(O)(NHC6H11) (L)
M[(C6H5)2P(O)(NHC6H11)] (C1)
M[(C6H5)2P(O)(NHC6H11)] (C2)
(C6H5)P(O)(NHC6H11)2 (Ĺ)
M[(C6H5)P(O)(NHC6H11)2]2 (Ć1)
M[(C6H5)P(O)(NHC6H11)2]2 (Ć2)
Doxorubicin
This work
This work
79 0.09
62 0.03
105 0.07
92 0.09
This work
[13]
129.5 0.01
101.2 0.17
93.2 0.03
40 0.08
537.1 0.05
300.9 0.08
115.4 0.10
17 0.07
[13]
[13]
This work
Results represent mean SD of at three independent experiments. SD represents the standard deviation. M = SnCl2(CH3)2.

4 of 14
DOROSTI AND MOHAMMADPOUR
(ATCC 25923), and two Gram‐negative bacteria, namely
E. coli (ATCC 25922) and P. aeruginosa (ATCC 27853).
Base plates were prepared by pouring autoclaved
Mueller‐Hinton agar into sterile petri dishes and allowing
them to settle. Compounds dissolved in DMSO at a con-
centration of 6000 μg ml−1 were used. Then, the solutions
of the compound tested were placed on the well of the
media inoculated with the microorganisms. The plates
were incubated at 35°C and 24 h for the microorganism
cultures. After incubation, the growth around the discs
was measured in terms of diameters of growth inhibition
zones (GIZs). The results are presented in Table 2. Genta-
micin was used as reference antibacterial drug. DMSO
was used as a solvent control.
The topological analysis of the electron charge density
performed for the title complex was carried out using
Bader's QTAIM.[22] The QTAIM analysis was performed
using the wave functions generated at the B3LYP/
LANL2DZ/6‐311G* level. NBO analysis was performed
at the same level of theory.[23]
2.6 | Synthesis
2.6.1 | Synthesis of N‐(cyclohexyl)
diphenylphosphonic amide (L)
A solution of 8 mM cyclohexylamine (23.8 mg) in 10 ml of
dry acetonitrile was added dropwise to a solution of 4 mM
diphenylphosphonic chloride (28.0 mg) in 20 ml of acetoni-
trile at 0 C. After 24 h stirring, the solvent was removed; the
product was washed with distilled water and dried.
2.4 | X‐ray Measurements
Yield: 65%; m.p. 154°C. 1H NMR (CDCl3, δ, ppm): 1.22
(m, 6H, CH2), 1.65 (t, 3J(H, H) = 4.37 Hz, 2H, CH2), 2.04 (d,
3J(H, H) = 8.36 Hz, 2H, CH2), 2.84 (d, 3J(H, H) = 6.19 Hz,
X‐ray data of compound C3 were collected using a Bruker
SMART 1000 CCD single‐crystal diffractometer with graph-
ite monochromated Mo Kα radiation (λ = 0.71073 Å). The
collected data were processed with the Bruker program
SAINT.[16] A multi‐scan type absorption correction was
applied using SADABS.[17] The structures were refined with
SHELXL‐2013 by full‐matrix least‐squares on F2.[18] The
positions of hydrogen atoms were obtained from the differ-
ence Fourier maps.
3
2
1H, CH), 2.99 (t, J(H,H) = J(P,H) = 5.20 Hz, 1H, NH),
3
3
7.44 (m, 6H, Ar─H), 7.89 (ddd, J(H, H) = 9.31 Hz, J(H,
H) = 7.97 Hz, J(P,H) = 1.55 Hz, 4H, Ar─H). 13C NMR
4
(CDCl3, δ, ppm): 25.29 (s), 25.49 (s), 36.78 (d, 2J(P,
3
C) = 4.91 Hz), 50.65 (s), 128.57 (d, J(P,C) = 12.45 Hz),
131.79 (d, 4J(P,C)
=
2.72 Hz), 132.21 (d, 2J(P,
C) = 9.40 Hz), 132.48 (1J(P,C) = 129.21 Hz). 31P NMR
(CDCl3, δ, ppm): 22.13 (m). FT‐IR (KBr, cm−1): 3442
(NH), 3126, 2927, 2855, 1438, 1203, 1184 (P═O), 1109,
1091, 995, 914, 722, 698, 573, 544, 518.
2.5 | Computational Details
DFT calculations were performed using the Gaussian03
program package.[19] An eight‐membered ring with two
hexa‐coordinated tin(IV) centres was extracted from the
X‐ray structure and fully optimized. All calculations were
carried out using the three‐parameter hybrid functional
B3LYP[20] in conjunction with the LANL2DZ[21] basis
set for Sn and the 6‐311+G* basis set for other elements
without any symmetry restrictions.
2.6.2 | Synthesis of N‐(cyclohexyl)
diphenylphosphonic amide dimethyl
tin(IV) dichloride in bulk form (C1)
(CH3)2SnCl2 (12.5 mM, 27 mg) was added to a solution of
25 mM L (75 mg) in 10 ml of toluene and heated (60–
TABLE 2 Mean diameter of inhibition zone as a criterion of antibacterial activities of the synthesized compounds
Gram‐negative bacteria Gram‐positive bacteria
Compound
P. aeruginosa
E. coli
S. aureus
B. subtilis
B. cereus
Ref.
(C6H5)2P(O)(NHC6H11) (L)
M[(C6H5)2P(O)(NHC6H11)] (C1)
M[(C6H5)2P(O)(NHC6H11)] (C2)
(C6H5)P(O)(NHC6H11)2 (Ĺ)
M[(C6H5) P (O)(NHC6H11)2]2 (Ć1)
M[(C6H5) P (O)(NHC6H11)2]2 (Ć2)
Gentamicin
13
12
20
—
12
14
20
11
14
21
—
10
14
20
13
14
18
—
15
18
20
12
18
23
10
20
21
23
9
This work
This work
15
21
10
15
20
20
This work
[13]
[13]
[13]
This work
The values indicate the diameters in mm for the growth inhibition zone observed after 24 h of incubation at 35°C. Error values are within 1 mm. Moderately
active (8–13); highly active (>14). M = SnCl2(CH3)2.

DOROSTI AND MOHAMMADPOUR
5 of 14
70°C) for 72 h. The solvent was slowly evaporated to give
a white powder.
(O)P(NHC6H11)], was obtained from the reaction of
(CH3)2SnCl2 with one molar equivalent of L. Bulk form
of compound C1 was obtained using a heat gradient
applied to a solution of the reagents in toluene and nano-
scale material C2 was obtained by ultrasonic irradiation
in an ethanolic solution (Scheme 1). The bulk form C1
was studied using FT‐IR and multinuclear NMR spectros-
copies. In the FT‐IR spectra, the P═O stretching vibration
of the ligand results in an absorption at 1184 cm−1, while
this band shifts to lower energy (1145 cm−1) for the
organotin(IV) complex. This negative shift indicates the
weakening of the P═O bond due to the coordination of
the phosphoryl oxygen atom to tin.[25a,b] The bands at
about 590 and 554 cm−1 correspond to antisymmetric
and symmetric stretching frequencies of Sn─C bonds. An
absorption appears at 453 cm−1 in the spectrum of the
complex, which is absent in the spectrum of the free
ligand. This is assigned to the Sn─O stretching mode.
The 1H NMR spectrum of the complex in CDCl3 solu-
tion is consistent with the formula of a 1:1 adduct, which
Yield: 40%; m.p. 325°C. Anal. Calcd for
C20H28Cl2NOPSn (519.03) (%): C, 46.28; H, 5.44; N, 2.70.
1
Found (%): C, 46.37; H, 5.41; N, 2.60. H NMR (CDCl3,
δ, ppm): 1.21 (s, 2J(119Sn,1H) = 59.92 Hz, 6H, Sn
3
(CH3)2), 1.27 (m, 6H, CH2), 1.57 (d, J(H, H) = 8.66 Hz,
3
2H, CH2), 2.0 (d, J(H, H) = 10.44 Hz, 2H, CH2), 2.96
(m, 1H, CH), 3.08 (m, 1H, NH), 7.45 (m, 6H, Ar─H), 7.8
3
3
(dd, J(H,H) = 7.79 Hz, J(H,H) = 4.24 Hz, 4H, Ar─H).
13C NMR (CDCl3, δ, ppm): 14.41 (s, (SnCH3),
1J(119Sn,13C) = 782.68 Hz), 24.36 (s), 25.24 (s), 31.01 (s),
2
3
36.58 (d, J(P,C) = 4.91 Hz), 50.87 (s), 128.72 (d, J(P,
4
C) = 12.68 Hz), 131.46 (d, J(P,C) = 2.72 Hz), 131.77 (d,
3J(P,C) = 10.18 Hz), 132.18 (d, 2J(P,C) = 9.66 Hz),
132.49 (d, 1J(P,C) = 117.59 Hz). 31P NMR (CDCl3, δ,
ppm): 23.12. 119Sn NMR (CDCl3, δ, ppm): −142.76. FT‐
IR (KBr, cm−1): 3445 (NH), 2923, 1482, 1437, 1145
(P═O), 1130, 1046, 1022, 997, 791, 754, 728, 692, 590
(Sn─C)as, 554 (Sn─C)s, 534, 453 (Sn─O).
2
1
exhibits a tin–proton coupling constant J(119Sn, H) of
about 59.92 Hz, falling in the range for five‐coordinated
dimethyltin(IV) species.[8b,25] Also, the peak integrals
indicate that the Sn atom is five‐coordinated. The methy-
lene protons of the aliphatic ring of (C6H5)2P(O)
(NHC6H11) appear in CDCl3 as multiplet at 1.27 and
2.96 ppm and as two different doublets at 1.57 and
2.0 ppm (3JHH = 8.66 and 10.44 Hz, respectively). For N‐
(cyclohexyl)diphenylphosphonic amide, a triplet peak is
observed for the amino protons at 2.99 ppm (in CDCl3)
which is appeared at 3.08 ppm as a multiplet peak for
C1. In the 13C NMR spectra, signals for the aryl carbons
except for the ipso carbons are slightly shifted to low field
compared with the free ligand in CDCl3 solution; the shift
is a consequence of an electron density transfer from
ligand to metal atom. Also, the coupling between phos-
phorus and ortho and meta carbons is observed as these
values (nJPC, n = 2, 3) are larger for the complexed ligand
than the free one. The value of the coupling constant
1J(119Sn–13C) for the complex, 782.68 Hz, is indicative of
a five‐coordinated compound.[25a,26] Chemical shifts of
31P NMR spectrum for the complex are quite similar to
those of the corresponding ligand. These data do not pro-
vide any concrete information about the tin–ligand coor-
dination. However, the single resonance at −142.76 ppm
in the 119Sn NMR spectrum of the complex in CDCl3
solution provides additional support for five‐coordinated
tin atoms in this solution.[25b,27]
2.6.3 | Synthesis of N‐(cyclohexyl)
diphenylphosphonic amide dimethyl
tin(IV) dichloride at nanoscale (C2)
A solution of 0.4 M (CH3)2SnCl2 in 20 ml of ethanol was
poured dropwise into a suspension of 0.8 M L under
ultrasonic irradiation (53 Hz) for 90 min. The obtained
precipitates were filtered off, washed with water and then
dried in air. Yield: 47%; m.p. 325°C. Calculated (%): C,
46.28; H, 5.44; N, 2.70. Found (%): C, 46.31; H, 5.48; N,
2.63. FT‐IR (KBr, cm−1): 3443 (NH), 2927, 1483, 1437,
1144 (P═O), 1130, 1049, 1023, 999, 793, 754, 729, 694,
590 (Sn─C)as, 559 (Sn─C)s, 535, 454 (Sn─O).
2.6.4 | Synthesis of {(Sn(CH3)2)2[μ‐OP(O)
(C6H5)2]2}n (C3)
This complex was prepared using the branched tube
method.[24] Sn(CH3)2Cl2 (0.36 g, 1 mmol) and L (0.416 g,
2 mmol) were placed in the main arm of a branched tube.
Ethanol–water was carefully added to fill arms, the tube
sealed and the ligand‐ and metal‐containing arm immersed
in a bath at 60°C while the other was at ambient tempera-
ture. After 5 days, colourless crystals deposited in the
cooler arm were isolated, filtered off and dried.
3 | RESULTS AND DISCUSSION
3.1 | Spectroscopic Studies
3.2 | Structural Analysis of Nanostructure C2
Synthesis of L was performed according to Section 2 and a
new five‐coordinate Sn(IV) complex, Sn(CH3)2Cl2[(C6H5)2
The approach used in the synthesis of nanomaterial C2 is
sonochemistry. In this method, application of powerful

6 of 14
DOROSTI AND MOHAMMADPOUR
ultrasound radiation and the instantaneous formation of a
plethora of crystallization nuclei results in the formation of
nanoscale compounds.[28] Comparing the FT‐IR and UV–
visible spectra for the bulk form (C1) and nanoscale form
(C2) reveals that the compound at the two sizes is identical.
The FT‐IR spectra show a relatively broad band at around
3443 cm−1, assigned to N─H modes (Figure S1). The C─H
modes involving the aliphatic hydrogen atoms of the
ligand produce a band at around 2927 cm−1. Absorption
band with medium intensity at around 1437 cm−1 corre-
sponds to vibration of the phenyl moiety of ligand. The
band corresponding to ν(PO) vibration is found at
1144 cm−1. The bands at about 590 and 535 cm−1 corre-
spond to antisymmetric and symmetric stretching
frequencies of Sn─C bonds, and the weak band at
454 cm−1 is assigned to the Sn─O stretching mode.
Figure 1 shows the UV–visible spectrum of the tin(IV)
complex dissolved in ethanol. The absorption bands in
the UV region are observed at wavelengths of about
243, 265 and 271 nm which can be attributed to the
interligand π → π* and n → π* transitions. It is clearly
seen that the UV–visible spectrum of the complex is very
similar for both scales.
Acceptable matches, with slight differences in 2θ, were
observed between the X‐ray diffraction patterns of bulk
form (C1) and nanoscale form (C2). These results indicate
that the obtained compound in bulk and nanoscale forms
is the same. The morphology, structure and size of C2
were investigated using SEM. As shown in Figure 3(a),
a combination of rod and spherical nanostructures in eth-
anol solvent was obtained. To achieve a uniform distribu-
tion of nanostructures, a few drops of DMSO were added
to an ethanolic solution of the complex and monodisperse
distribution of nanorods with a diameter of about
80–90 nm was obtained (Figure 3c).
The EDS spectrum of the nanoscale C2 is depicted in
Figure S2(a). This spectrum shows a major peak of ele-
mental tin at around 3.5 keV, which is in accordance with
the main identification line of metallic tin nanoparticles.
Peaks with variable intensity of C, O, Cl, N and P also
arise due to the presence of these atoms in complex C2.
EDS analysis confirmed the formation of C2 consisting
of tin–phosphonic amide nanorods. Quantitative analysis
elucidated that C, O, P, N, Cl and Sn elements were pres-
ent in amounts of 63.71, 14.20, 5.92, 9.95, 0.06 and
6.61 wt%, respectively. Elemental mapping of tin is
depicted in Figure S2(b), which confirms the uniform dis-
tribution of Sn throughout the sample and its prevalent
presence.
The X‐ray diffraction patterns of the compound in
bulk and nanoscale forms are shown in Figure 2.
In order to examine the thermal stability of the nano-
scale compound, thermogravimetric analysis (TGA) and
differential thermal analysis (DTA) were carried out
between 30 and 800°C (Figure 4). The TGA curve of this
compound indicates that it does not melt and is stable up
to 205°C, at which temperature it begins to decompose.
Removal of the methyl and chlorine groups and decom-
position of the ligand take place in three thermal steps
in the range between 205 and 465°C with two very small
endothermic effects at 220 and 410°C, ultimately giving a
bold solid (observed: 54.27%; calcd: 56.38%).
SEM image and the corresponding particle size distri-
bution histogram of the residue obtained from the calci-
nation of C2 at 650°C also show that a product with a
FIGURE 1 UV–visible absorption spectra of complex in bulk
form and nanoscale form.
FIGURE 2 X‐ray diffraction patterns of
bulk form and nanoscale form of
Sn(CH3)2Cl2[(C6H5)2(O)P(NHC6H11)].

DOROSTI AND MOHAMMADPOUR
7 of 14
FIGURE 3 SEM images of nanoparticles of C2 prepared in (a) ethanol and (b) ethanol–DMSO. (c) Corresponding particle size distribution
histogram.
In the next step, in order to have a comparison
between the resulting SnP2O7 products, calcination of
bulk form C1 was done at 650°C for 4 h. Figure 5(b)
shows the SEM image of the resulting SnP2O7 with a
nanostructural surface and diameters between 40 and
100 nm. The difference between the sizes of the two
SnP2O7 nanostructures originated from the different ini-
tial precursor of complexes C1 and C2. This point empha-
sizes that the particle size of tin‐based complex is an
important factor in the produced nanoscale materials in
bulk form and nanostructural form.
3.3 | Cytotoxic Activity
FIGURE 4 Thermal behaviour of nanostructured C2.
Recently, organometallic complexes have been attracting
nanostructural surface was formed (Figure 5a). These
nanoparticles have diameters between 20 and 60 nm,
but the frequency of 30–40 nm diameter nanoparticles is
higher than those outside this range. The elemental com-
positional analysis of the synthesized nanostructure was
carried out using EDS as shown in Figure S3(a). The pres-
ence of major emission peak at round 3.5 keV indicates a
characteristic signal for nanosized particles of tin, as well
as variable intense peaks of O and P being observed. Fig-
ure S3(b) displays the elemental mapping of the nano-
rods. It confirms the homogeneous distribution of all
the elements throughout the sample. EDS analysis and
mass loss calculations suggest that the final decomposi-
tion product is SnP2O7.
growing interest in cancer therapy. Hence, in order to
compare the cytotoxicity of the compounds under investi-
gation in this work (L, C1 and C2), preliminary in vitro
cell experiments were performed using MTT assay[29]
for 24 and 48 h with A2780 and PC‐3 cancer cell lines.
As seen in Figure 6, increasing the incubation time from
24 to 48 h shows a considerable decrease in the cell viabil-
ity for the selected compounds against both cell lines.
Further, the results of the in vitro cytotoxic effects of these
compounds against the two tumour cell lines are pre-
sented in Table 1 and compared using doxorubicin as a
standard drug. Note that complexes C1 and C2 showed
higher cytotoxicity against both cell lines in comparison
to the free ligand (L: 93 μM; C1: 79 μM; C2: 62 μM

8 of 14
DOROSTI AND MOHAMMADPOUR
FIGURE 5 SEM images of (a) nanoparticles produced by calcination of bulk form C1 and (b) rod‐like nanostructure C2, and their
corresponding particle size distribution histograms.
tin(IV) complexes containing semicarbazonates have IC50
values in the nM range towards A253, A549 and DLD‐1
cell lines,[30] as well as dinuclear organotin(IV) complexes
having IC50 values of 0.1–100 μM for a number of human
tumour cell lines.[31] Notably, the IC50 values of a tin–
phosphorictriamide complex against some tumour cell
lines (Hela, PC‐3, MCF‐7 in the range 99.8–1150 μM) have
been reported in the literature,[32] which are higher than
the IC50 values determined in this study of Sn(IV) com-
plexes for the tested cell lines. It can also be seen from
Table 1 that compared with ligand L and bulk complex
C1, the cytotoxicity of nanoscale complex C2 against
A2780 shows a 1.5‐ and 1.3‐fold increase, which is similar
to the results of our previously reported nano‐diorganotin
complex.[13] Similarly, for the PC‐3 tumour cell line,
nanosize C2 displays lower IC50 values than free ligand L
and bulk form C1. Note that the IC50 value for nanoscale
C2 against PC‐3 reaches 92 μM which is an improvement
of approximately 1.36 and 1.14 times compared with that
for L (125 μM) and C1 (105 μM). It is well known that
shape, size, surface modification and intrinsic properties
are parameters that affect the cytotoxicity of nanoparti-
cles.[33] In addition, lack of selectivity towards tumour cells
FIGURE 6 Cytotoxic effect of L, C1 and C2 against A2780 and
PC‐3 cell lines at 1.0 × 10−4 M.
is responsible for dose‐limiting side effects. Hence, to study
the degree of selectivity in the cytotoxic activity of the com-
pounds, assays using lymphocyte isolation from whole
towards A2780 cell line; L: 125 μM; C1: 105 μM; C2: 92 μM
towards PC‐3 cell line), which are in agreement with those
of reported organotin(IV) complexes. For example, some
human blood were carried out on bulk form C1 and nano-
scale C2, which showed survival values were 87 and 90%
for these forms, respectively. Therefore, the nanoscale

DOROSTI AND MOHAMMADPOUR
9 of 14
tin(IV) complex C2 may be a potential chemotherapeutic
candidate that can avoid the pollution problem of
organotin drugs.
(Table S1).[13] To determine structure–activity relation-
ships in these compounds, quantum chemical computa-
tions (DFT) were performed to obtain the electronic
factors including the energies of highest occupied molecu-
lar orbital (EHOMO) and lowest unoccupied molecular
orbital (ELUMO), the net atomic charges (Q) and the struc-
tural descriptors such as dipole moment (μ), hydrophobic
coefficient (log P) and molecular volume (Mv). A compar-
ison between compounds L and Ĺ indicates that their
structural difference is only the replacement of a phenyl
group in L with a cyclohexylamine group in Ĺ. This causes
the phosphorus atom in L to be more positive than in Ĺ
(electronic and steric effects that cause smaller IC50 for
L). Similarly, δ(31P) are more positive in C1 than in Ć1
(electronic effect leading to much smaller IC50 values for
C1). In addition, the frontier molecular orbital (HOMO
and LUMO) energies are the most significant properties,
which are related to a molecule's reactivity. HOMO energy
is closely related to reactivity to electrophilic attack while
LUMO energy is closely related to reactivity to nucleo-
philic attack. Compound C1, which exhibited the lowest
HOMO and LUMO energies (EHOMO = −0.25588,
ELUMO = −0.06143) compared to Ć1 (EHOMO = −0.22618,
ELUMO = −0.03644), revealed the highest anticancer activ-
ity against the two investigated cell lines. A comparison
between Mv values shows that the bulkiness of C1
(Mv = 319.67 cm3 mol−1) is considerably lower than that
of Ć1 (Mv = 575.75 cm3 mol−1) and this is the reverse order
of their activity. Another important factor to be considered
is log P, which was calculated using Hyperchem 7.0 soft-
ware, being −2.26 and −30.61 for C1 and Ć1, respectively.
Therefore, the more lipophilic nature of complex C1 con-
ceivably plays a role in its higher cytotoxicity. Similarly,
for the tested bacteria, L and C1 display higher activity
than Ĺ and Ć1 (GIZ: 9–13 mm in L, 10 mm in Ĺ; 12–
23 mm in C1, 10–21 mm in Ć1). These results obtained
from this investigation can be utilized as guidelines for fur-
ther improvement of anticancer and antibacterial agents.
3.4 | Antimicrobial Activity
A search of the literature reveals that tin exhibits outstand-
ing antibacterial properties that would lead to biomedical
applications.[33c] Here, L, C1 and C2 were screened to eval-
uate their antimicrobial activity against B. cereus, B.
subtilis, S. aureus, E. coli and P. aeruginosa using the cup‐
plate agar method. The commercial antibiotic gentamicin
was used as positive control and the results of the assays
are presented in Table 2. Based on the GIZ values, L has
moderate activity against all of the tested bacteria. It is also
observed that organometallic complexes C1 and C2 show
higher activity than L against these bacteria (GIZ: 9–
13 mm for L, 12–18 mm for C1, 18–23 mm for C2). These
results are in keeping with those for other organotin(IV)
compounds. The excellent in vitro antibacterial activities
[32]
of Sn(CH3)2Cl2(4‐NC5H4CONHPO(NCH3CH2C6H5)2)2
and tin complexes of two phosphonic diamides (as O‐
donor ligands)[25a] have been reported against some
Gram‐positive and Gram‐negative bacteria. Also, nano-
scale complex C2 had greater antimicrobial activity than
its bulk form against the selected bacteria. Although the
mechanism of toxicity of nanostructured compounds is
very complicated, this is probably due to the increased sur-
face‐to‐volume ratio of particles which may play an impor-
tant role in the antibacterial activity.[34] The GIZ values
indicate that B. subtilis was more sensitive to nanoscale
C2 than the other studied bacteria. The present investiga-
tions revealed that nanosize compound activity is close to
those of the control drug.
3.5 | Structure–Activity Relationships
It is important to understand the role of the chemical
framework in prompting biological activity. Hence, the
structure–activity relationship was investigated in order
to explore physicochemical properties that could be corre-
lated to the biological activity of a molecule.[35] In our pre-
vious works, structure–activity relationship studies were
performed with some diazaphosphore derivatives relating
to their anticancer activities and it was shown that the
electronic properties are the most effective factors for bio-
logical potency of the studied compounds.[36] Here, ligand
L that contains a cyclohexylamine and two phenyl groups
attached to phosphorus atom and its five‐coordinated
complex C1 showed higher cytotoxic activity than ligand
Ĺ with a phenyl and two cyclohexylamine substituents
and its six‐coordinated complex Ć1, respectively. The syn-
thesis of Ĺ and Ć1 was reported in our previous paper
3.6 | X‐ray Crystallography
In this work, we were interested in the structure of C1 as
determined using X‐ray crystallography. However, in spite
of all attempts, this complex could not be obtained in the
crystalline state. Unexpectedly, the reaction of 1 equiv. of
L with 1 equiv. of Sn(CH3)2Cl2 afforded colourless crystals
of C3 which were grown from an ethanol–water solution
in a branched tube, whereas these single crystals were pre-
viously prepared by the reaction of (CH3)2SnCl2 with
HO2PPh2 in a 1:2 molar proportion in methanol.[37] C3
crystallizes in space group C2/c with four discrete mole-
cules in the unit cell. The crystalline compound C3 shows
disorder in one of the phenyl groups over two positions

10 of 14
DOROSTI AND MOHAMMADPOUR
TABLE 3 Structural data and refinement parameters for
{(Sn(CH3)2)2[μ‐OP(O)(C6H5)2]2}n (C3)
with relative occupancies of 0.501/0.499. Crystal data and
details of the X‐ray analysis are given in Table 3. Selected
bond lengths and angles are summarized in Table S2.
Molecular structure of compound C3 is shown in Fig-
ure 7(a). The crystal structure of complex C3 consists of
one‐dimensional polymeric units of diphenylphosphinate.
The complex contains a hexa‐coordinated tin atom
bridged by ‘(C6H5)2(O)PO−’, so two eight‐membered rings
around tin are formed. Identical ligands (the two methyl
groups and the four phosphonic oxygen atoms) are in
trans positions and the trans bond angles around Sn atom
are 180°. The different ligands are cis to each other and
C(13)–Sn–O(1) and C(13)–Sn–O(2) bond angles are in
the range 86.36–93.64° (Table S2). The SnO4 system is
coplanar (∑(O–Sn–O) = 360°) with trans O–Sn–O angles
of 180°. The two Sn─C bonds are collinear (C(13)–Sn–
C(13) = 180°) and almost perpendicular to the SnO4 plane
(O–Sn–C range 86.36–93.64°). A similar behaviour was
observed for other reported complexes.[38] The Sn─C bond
lengths are 2.106(2) Å, which are consistent with those
reported for other organotin(IV) complexes.[8b,25a,39] Two
different Sn─O distances (2.192(14) and 2.204(13) Å) and
also two different P–O–Sn angles (143.22(9)° and
143.44(10)°) can be observed in C3. The shorter Sn─O dis-
tances correspond to the larger P–O–Sn angles (and vice
versa). These Sn─O bond lengths are a little longer than
the Sn─O covalent bond lengths (2.038–2.115 Å).[38] There
are also C─H…π interactions with H…centroid distances
of 2.964 and 3.005 Å between two phenyl rings and hydro-
gen of methyl group with phenyl ring, respectively. The
H…H intermolecular interactions expand one‐dimen-
sional chains to a two‐dimensional supramolecular archi-
tecture (Figure 7b).
Formula
C26H26O4P2Sn
Formula weight
T (K)
583.10
147(2)
λ (Ǻ)
0.71073
Monoclinic
C2/c
Crystal system
Space group
Unit cell dimensions
a = 25.1749(19) Ǻ, α = 90°
b = 9.6631(7) Ǻ, β = 98.374(3)°
c = 10.4280(9) Ǻ, γ = 90°
V (Å3)
2509.7(3)
4
Z
Dcalc (Mg m−3
)
1.543
1.175
Absorption
coefficient (mm−1
)
F (000)
Crystal size (mm3)
1176
0.180 × 0.020 × 0.020
2.261–27.577
Theta range for data
collection (°)
Index ranges
−31 ≤ h ≤ 32, −12 ≤ k ≤ 12,
−13 ≤ l ≤ 13
Reflections collected
Independent reflections
Rint
16 206
2906
0.0379
100.0
Completeness to theta (%)
Absorption correction
Semi‐empirical from
equivalents
Maximum and minimum
transmission
0.7457 and 0.6570
Refinement method
Full‐matrix least‐squares on F 2
2906/1/177
Data/restraints/parameters
Goodness‐of‐fit on F 2
Final R indices [I > 2σ(I)]
R indices (all data)
3.7 | QTAIM Analysis
1.037
Detailed information about the strength and nature of
Sn…O interaction can be obtained by topological analysis
of the electron densities. Application of QTAIM to com-
plex C3 allowed us to find bond critical points (BCPs)
and analyse their properties (electron density, ρBCP, its
R1 = 0.0216, wR2 = 0.0455
R1 = 0.0360, wR2 = 0.0499
0.823 and −0.457
Largest difference peak and
hole (e Å−3
)
2
Laplacian, ▽ ρBCP, and total electronic energy density,
2
HBCP). Table S3 presents the values of ρBCP, ▽ ρBCP
and HBCP computed at the Sn─O BCPs. In QTAIM anal-
ysis, large values of ρBCP, ▽ ρBCP < 0 and HBCP < 0 refer
kinetic and potential energy densities, respectively. The
2
values of ρ at the Sn─O BCPs are small in the range
2
to shared interactions (covalent bonds); small values of
0.063–0.066 au and the corresponding ▽ ρBCP values
2
are all positive, in the range 0.261–0.276 au. These values
are consistent with closed‐shell interactions in this sys-
tem.[40] Despite falling in a region of charge depletion
ρ
BCP, ▽ ρBCP > 0 and HBCP > 0 are calculated for
closed‐shell interactions (ionic, hydrogen bonds and van
2
der Waals interactions); and ▽ ρBCP > 0 and HBCP < 0
2
are assigned to the intermediate ones.[19] The electronic
energy density is obtained from the equation
HBCP = GBCP + VBCP, where GBCP and VBCP are the local
with ▽ ρBCP > 0, the small negative values of HBCP show
that the potential energy slightly overcomes the kinetic
energy at these BCPs and the interactions are principally

DOROSTI AND MOHAMMADPOUR
11 of 14
FIGURE 8 Hirshfeld surfaces mapped with dnorm of C3.
natural charges and electronic configurations of selected
atoms are presented in Table 4. Based on the NBO results,
calculated natural charge on O atoms coordinated to Sn is
−1.18 and 2.20 for P atom (Table 4). The electron config-
uration of Sn atoms is [core]5s0.835p0.736p0.01 and
[core]5s0.805p0.736p0.01. Therefore, 46 core electrons, 1.56
and 1.54 valence electrons (on 5s and 5p atomic orbitals)
and 0.01 Rydberg electrons (on extra valence 6p orbital)
give a total of 47.56 and 47.54 electrons, which is in agree-
ment with the calculated natural charge (+2.43 and
+2.46) on Sn atoms in C3. In the NBO method, the
strength of delocalization of electron density between
occupied Lewis‐type orbitals and formally unoccupied
non‐Lewis orbitals (antibonding or Rydberg) can be esti-
mated using the second‐order perturbation theory. These
electron delocalizations correspond to stabilizing donor–
acceptor interactions.[41] NBO analysis of C3 presents
Sn─C natural bond orbitals for Sn and two methyl groups
occupied by 1.95 electrons and polarized towards the C
atoms (ca 76%). The interaction of Sn with O atoms of
phosphate can be illustrated as donation of electron den-
sity from lone pair orbitals (LP) on donor atoms to accep-
tor tin orbitals. Electron donations from lone pairs of
FIGURE 7 (a) ORTEP diagram (at the 50% probability level) of
C3, with hydrogen atoms omitted for clarity. (b) Two‐dimensional
structure produced by C&bond;H…H&bond;C intermolecular
interactions (the dashed green and blue lines show C&bond;
Hmethyl…π and C&bond;Hphenyl…π interactions in C3, respectively).
electrostatic in nature with a small amount of Sn…O
covalent interaction.
3.8 | NBO Analysis
NBO analysis was performed to supply an in depth
insight into the electronic structure of C3. The calculated
TABLE 4 Calculated natural charges and natural electron configuration (NEC) for selected atoms and hybridization of donor lone pairs
Atomic charge
NEC
OP&dbond;O
Hybridization
LP (OP&dbond;O)
Compound
q (OP&dbond;O
)
q (P)in
q (Sn)
C3
−1.18 (O159, O160
O162, O163) −1.20
(O55, O108), −1.19
,
2.20, 2.16, 2.06
2.43 (Sn53),
2.46 (Sn106
[Core]2s1.762p5.41
(O55, O83, O136
O159, O160,
sp1.18 (O159, O163), sp1.23
(O160, O108), sp1.73
(O55, O108), sp1.49
)
,
(O83, O136
)
O162, O163
)
(O83, O136)

12 of 14
DOROSTI AND MOHAMMADPOUR
FIGURE 9 Two‐dimensional fingerprint plots, full and resolved into C…H/H…C, Sn…O/O…Sn, O…H/H…O, H…H and O…O contacts
showing percentages of contacts contributed to the total Hirshfeld surface area of the molecule.
oxygen (LP (O)) to the acceptor orbitals of Sn, 5p (Sn),
with stabilization energies of 27.39 and 21.35 kcal mol−1
respectively, are the strongest interactions observed
between ligand and tin atom.
The two‐dimensional fingerprint plots are used for identi-
fication and separation of intermolecular interactions, and
relative contribution of these interactions can be obtained
from the area of the surfaces.[44] Figure 9 illustrates the
breakdown of two‐dimensional fingerprint plots of the
Hirshfeld surfaces for the crystalline complex. With these
analyses, different interactions can be separated, including
H…H, C…H, O…H, Sn…O and O…O, which commonly
overlap in full fingerprint plots. H…H (53.1%) and C…H
(27.5%) contacts have the highest share of Hirshfeld sur-
face. H…H interactions appear as a very distinct spike on
the diagonal of the plot in Figure 9 (top row, centre). They
have the lowest value of de + di in compound C3 (1.4 Å).
C…H/H…C contacts comprise 15.7 and 11.8% of the surface
for molecule C3 (top row, right). The interaction of the O
atoms with the Sn atom comprises a medium share of the
Hirshfeld surface (7.4%) and appear as wings on the top left
(O…Sn) and bottom right (Sn…O) of the two‐dimensional
fingerprint plots (bottom row, left). O...H and O…O con-
tacts appear in the central region of the plots and they com-
prise area fractions of 5.9 and 2.8% in C3 (Figure 9, bottom
row, centre and right).
,
3.9 | Hirshfeld Surface Analysis
Hirshfeld surface analysis was used to explore the intermo-
lecular interactions[42] and the related proportions of
asymmetric unit of complex C3. The Hirshfeld surfaces
mapped with dnorm range of −0.906 to 1.652 Å (Figure 8),
and full fingerprint plot along with the decomposed ones
(Figure 9) were generated using the program CRYSTAL
EXPLORER 3.0,[43] which accepts a structure input file in
the CIF format. The dnorm surface of C3 contains several
large red regions. One visible red region on the Sn atom
and another on the phosphoryl O atom are due to the
Sn…O interactions to form a dimer molecule, labelled as
1a and 1b. Also, two other interactions of Sn atom with O
atoms in the neighbouring structure unit, based on which
the polymeric structure of the complex is constructed, are
visible as large light red regions (in another orientation
of the molecule, Figure S4). One remaining visible red
region on the Sn atom refers to Sn…C interaction labelled
as 2. In addition, H…H interactions are observed as rela-
tively light red spots around the hydrogen atoms on one
of the coordinate phenyl rings to phosphor labelled as 3.
4 | CONCLUSIONS
We have synthesized and characterized a new five‐coordi-
nated diorganotin(IV) complex, [Sn(CH3)2Cl2L], in bulk

DOROSTI AND MOHAMMADPOUR
13 of 14
form (C1) and nanoscale form (C2) by a slow evaporation
approach and a sonochemical method, respectively. The
morphology of C2 prepared sonochemically is a nanocrys-
talline rod shape. The results of TGA–DTA and SEM–EDS
show that the obtained nanopowders via calcination of C2
at 650°C are SnP2O7 with spherical morphology and size of
about 30–40 nm. Complexes C1 and C2 and the corre-
sponding ligand have been investigated as cytotoxic agents
against two cancer cell lines, A2780 and PC‐3, using the
MTT method. The IC50 values indicate that the new Sn(IV)
complexes have a strong antitumour activity and nano-
structured C2 is more cytotoxic than its bulk form. Also,
the results of antimicrobial assays show that the new com-
plexes have antibacterial effect against Gram‐negative and
Gram‐positive bacteria with higher activity for nanoscale
C2. Comparing in vitro data for the synthesized compounds
in this work and our previous research reveals that the
obtained biological data can be attributed to the different
structures and different substituents on the ligand of these
complexes. The lowest value of HOMO and LUMO
energies and more lipophilic nature of C1 (complex in this
work) might be considered as a reason for its higher
biological activity in comparison with complex Ć1 in our
previous work. Crystal structure analysis of C3 revealed
an octahedral geometry around the Sn(IV) with
diphenylphosphinate ions bonded to the metal through
OP atoms. Intermolecular interactions, supported by
Hirshfeld surface analysis, connect the one‐dimensional
chains to a two‐dimensional supramolecular network.
According to QTAIM analysis, the Sn…O interactions are
mainly electrostatic in nature with partial amount of Sn…
O covalent interaction. On the basis of NBO analysis, the
metal–ligand interaction is determined as charge transfer
between donor atoms of ligand and Sn(IV) ion.
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ORCID
Niloufar Dorosti http://orcid.org/0000-0003-3822-8214

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