Sonication-assisted synthesis of a strawberry-like nano-structure triphenyltin(IV) adduct as precursor for preparation of nano-sized SnP2O7: Crystal structure and DFT calculations

Article abstract of DOI:10.1016/j.molstruc.2020.129630

A triphenyltin(IV) adduct of phosphoramide with a formula of [Sn(Ph)₃Cl(L1)] (C1), L1 = N-phenyl-N′,N′′-bis(pentamethylene) phosphoric triamide, has been synthesized and characterized by elemental analyses and IR spectroscopy. In the crystal st

Full text of DOI:10.1016/j.molstruc.2020.129630

Journal of Molecular Structure 1230 (2021) 129630
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Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstr
Sonication-assisted synthesis of a strawberry-like nano-structure
triphenyltin(IV) adduct as precursor for preparation of nano-sized
SnP2O7: Crystal structure and DFT calculations
Mahtab Alipoura, Niloufar Dorostia,∗, Maciej Kubickib
a Department of Chemistry, Faculty of Science, Lorestan University, 68135-465, Khorramabad, Iran
b Department of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
A triphenyltin(IV) adduct of phosphoramide with a formula of [Sn(Ph)3Cl(L1)] (C1), L1 = N-phenyl-
´
Received 1 September 2020
Revised 26 October 2020
Accepted 9 November 2020
Available online 12 November 2020
N,N´-bis(pentamethylene) phosphoric triamide, has been synthesized and characterized by elemental
´
analyses and IR spectroscopy. In the crystal structure, the tin(IV) environment adopts a distorted trig-
onal bipyramidal geometry with three phenyl groups in the equatorial plane, one chloro atom and the
oxygen atom of ligand at the axial sites. Hirshfeld surface analysis and fingerprint plots were used to
investigat of the intermolecular interactions, responsible for the crystal architecture. The complex was
also prepared under ultrasonic irradiation (C1a) and characterized by elemental analyses, IR, and X-ray
powder diffraction (XRPD). The effects of two different concentrations of initial reagents on the size and
morphology of the nanomaterial were studied by scanning electron microscopy (SEM), which shows that
C1a grown as nano-strawberry morphology. The calcination of triorganotin complex in air atmosphere led
to production of nano-structured tin pyrophosphate. The thermal stabilities of the single crystal and of
the nano-crystalline form were investigated by thermal gravimetric and differential thermal analyses. The
structural and electronic properties of L1, C1 and similar molecules were evaluated by density functional
theory (DFT) calculations. Parameters derived from NBO and QTAIM analyses suggest that the nature of
Sn-O interaction is electrostatic with a small amount of covalent character and donor-acceptor delocal-
ization from the ligand oxygen atom to the tin center. Moreover, the electronic parameters including
HOMO-LUMO orbitals, bond gap, chemical hardness-softness, electronegativity, and electrophilicity were
calculated.
Keywords:
Triorganotin
Crystal structure
Nanostrawberry
DFT calculations
Hirshfeld surface
© 2020 Elsevier B.V. All rights reserved.
1. Introduction
properties, as well as to their application as cholinesterase [9] in-
hibitors.
Organotin(IV) complexes have attracted continuous and increas-
ing interest in coordination chemistry due to their different ap-
plications. They have been used, for instance, as efficient catalysts
[1], biological agents [2], and agrochemical fungicides and biocides
[3]. These materials also display many interesting nonlinear opti-
cal properties and therefore can be used in various photonic ap-
plications [4]. Coordination chemistry of organotin(IV) complexes
with phosphoramide ligands has frequently been studied and in-
dicated six and five-coordinated structures [[5], [7]]. Nowadays,
tin-phosphoramide complexes have become the subject of diverse
studies due to their antitumor [[6],[8]] and antibacterial [[7], [8]]
Preparation of nano-sized materials has been of particularly
great interest due to the eminent properties which can be obtained
at this scale, for instance large specific surface, which leads to the
enhanced optical [10], electrical [11] and a plethora of medical ap-
plications [12]. In contrast to widely studied inorganic nanoma-
terials, the specific syntheses of metal coordination complexes at
nano-scale seem to be surprisingly sparse, and to date most in-
vestigations on supramolecular coordination complexes have been
carried out only in the solid-state and therefore the studies of their
properties were limited to the investigations at the macroscopic
scale. The potential use of supramolecular coordination complexes
as materials for nanotechnological applications could be quite ex-
tensive, as the nanometer-scale materials often exhibit new and
interesting size-dependent physical and chemical properties that
cannot be observed in their bulk forms. For this reason, nano-
size coordination complexes are interesting candidates for applica-
∗
Corresponding author.
E-mail address: dorosti.n@lu.ac.ir (N. Dorosti).
https://doi.org/10.1016/j.molstruc.2020.129630
0022-2860/© 2020 Elsevier B.V. All rights reserved.

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Scheme 1. Formation of bulk form (C1) and nanostrawberry (C1a) complex as well as the SnP2O7 particles obtained from their calcination at 760°C.
tions in many fields, including nonlinear optics [13], sensor [14],
catalysis [15], magnetism, and molecular sensing [16]. Our re-
search group has recently reported synthesis of some nano-size
phosphoramide-based tin(IV) complexes, which improves product
biological activities [[9], [17]]. Additionally, SnP2O7 is an inorganic
crystalline material with a possible usage as an anhydrous proton
conductor in manufacturing fuel cells [18]. Despite the important
role of tin pyrophosphate nanopowders in the fabrication of fuel
cells, this compound was only prepared by coprecipitation method
so far [19], and studies on the synthesis of its nanostructures have
been lagging far behind. The use of organometallic compounds as
precursors for preparing inorganic nano-materials has been inves-
tigated [20]. In our previous work, SnP2O7 nanopowders were syn-
thesized by calcination method for the first time [21]. The size and
morphology of these nanomaterials are the two significant proper-
ties, depending on the kind of selected precursors for the prepa-
ration of them, which play a key role in technological applications
[22].
ent methods (Scheme 1). Crystal structure of C1 was determined
by X-ray crystallography and demonstrated a distorted trigonal-
bipyramidal geometry for Sn. An investigation of intermolecular in-
teractions in C1 via Hirshfeld surface analysis is also presented. Tin
phosphate nanostructures have been fabricated from this tin(IV)-
phosphoramides by the calcination method and a thermal decom-
position process.
On the other hand, the computational chemistry methods have
become increasingly important as a supplement, if not a substi-
tute, for the empirical methods in almost all areas of chemistry.
Therefore, by using NBO and QTAIM analyses, we tried to get in-
sight into the electronic aspects of interactions in some crystalline
triorganotins (C1-C3), and into the nature of tin-ligand interaction.
2. Experimental
2.1. Materials and general methods
Continuing our previous works on the coordination chemistry
of phosphoramides with organotin compounds and studies on
the relationship between the tin(IV)-phosphoramides and the di-
mension of the resulting SnP2O7 nano-structure, we synthesized
a novel five-coordinated triorganotin complex with the formula
[Sn(Ph)3Cl(L1)] (L1: N-phenyl-N,N´-bis(pentamethylene) phospho-
All chemicals were purchased and used without further purifi-
cation. Infrared (IR) spectra were recorded on a Shimadzu FT-IR
8400S (Japan) with a temperature controlled high sensitivity de-
tector (DLATGS detector) and a resolution of 4 cm−1 in the scan
range 500–4000 cm-1 using KBr pellets. Elemental analysis was
–
performed on a Heraeus CHN O-RAPID analyzer. Melting points
´
´
ric triamide [23]) at two different sizes (C1 and C1a) by two differ-
were measured on an Electrothermal 9100 apparatus. Electronic
2

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
spectra were recorded by Varian, Cary 100 UV–Vis spectropho-
tometer in the range of 200–800 nm. The ultrasonic bath unit
(Elmasonic model P30H) with ultrasonic peak output 80 kHz and
100 W has been used for ultrasonic synthesis of the nanostruc-
tured complex. SEM images were obtained from a MIRA3 TES-
CAN field emission scanning electron microscope equipped with
a link Energy-Dispersive X-ray (EDX) analyzer. The X-ray diffrac-
tion pattern of dry nanomaterial powder was obtained using an
STOE STADIP diffractometer with monochromatized Cu Kα radia-
1070 (s), 1032 (m), 957 (s), 926 (s, P-N), 845 (m), 804 (m), 752
(s, P-N), 735 (s), 690 (s), 611 (m), 552 (m), 502 (m), 469 (m). UV–
Vis in ethanol: λmax = 229 nm (π→π∗), 280 nm (n→π∗).
2.4.2. Synthesis of [N-phenyl-N,N´-bis(pentamethylene) phosphoric
´
´
triamide] chloro triphenyltin(IV) (C1) by evaporation method
To a solution of ligand (0.5 mmol, 0.154 g) in 20 mL methanol,
triphenyltin (IV) chloride (0.5 mmol, 0.193 g) was added and
heated (60–70 C) for
a few hours and the resulting mixture
º
was then stirred at room temperature overnight. The obtained
solid white material was filtered and washed several times with
methanol. Suitable single crystals of C1 were obtained by recrys-
tallization from ethanol solution at room temperature.
Yield 45%, M.p. 229–230°C; Anal. Calc. for C34H41ClN3OPSn: C,
58.94; H, 5.96; N, 6.06%. Found: C, 58.87; H, 5.90; N, 6.21%. IR (KBr,
cm−1): 3269 (m, NH), 3058 (w), 2941 (m, CH), 2849 (w), 1745 (s,
=
˚
tion (λ = 1.54 A). The simulated XRD powder pattern based on
single-crystal data was prepared using Mercury software. Thermal
decomposition behavior was measured with a Perkin LMERS2 ap-
paratus between 20 and 800°C in a static nitrogen atmosphere.
2.2. Crystal structure determination
C
C), 1603 (m), 1493 (m), 1371 (w), 1337 (m), 1292 (s), 1209 (w),
Crystals suitable for X-ray crystallography were obtained
from ethanol at room temperature. X-ray data of complex C1
were collected on Rigaku Xcalibur four-circle diffractometer with
=
1145 (s, P O), 1072 (s), 1028 (w), 955 (s, P-N), 847 (w), 798 (w),
735 (s, P-N), 694 (s), 609 (w), 544 (w, Sn-C), 507 (m), 451(s), 449
(m, Sn-O). UV–Vis in ethanol: λmax = 229 nm (π→π∗), 280 nm
(n→π∗).
EOS CCD detector and graphite-monochromated MoK radiation
α
˚
(λ=0.71073 A). The data were corrected for Lorentz-polarization
as well as for absorption effects [24]. Precise unit-cell parameters
were determined by a least-squares fit of 6213 reflections of the
highest intensity, chosen from the whole experiment. The struc-
ture was solved with SHELXT [25] and refined with the full-matrix
least-squares procedure on F2 by SHELXL []. All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were placed
in idealized positions and refined as ‘riding model’ with isotropic
displacement parameters set at 1.2 times Ueq of appropriate car-
rier atoms. The structure is disordered (one of the phenyl groups
relative occupancies 0.65/0.35).
2.4.3. Synthesis of nanostrawberry [N-phenyl- N,
´
´
N´-bis(pentamethylene) phosphoric triamide] chloro triphenyltin(IV)
by a sonochemical process (C1a)
5 mL solution of N-phenyl-N,N´-bis(pentamethylene) phospho-
´
´
ric triamide (L1) (0.007 mmol, 0.0022 g) in ethanol was positioned
in an ultrasonic bath, operating at 80 kHz and 100 W. Into this
ethanolic solution, a 5 mL solution of (C6H5)3SnCl (0.007 mmol,
0.0027 g) in ethanol was added dropwise. After the end of the
titration, the solution was kept in the bath for a selected aging
time at ambient temperature. The obtained precipitates were fil-
tered off, subsequently washed with ethanol and then dried in air.
Yield 37%, M.p. 228–230°C; Anal. Calc. for C34H41ClN3OPSn: C,
58.94; H, 5.96; N, 6.06%. Found: C, 58.90; H, 6.01; N, 6.10%. IR (KBr,
cm−1): 3263 (m, NH), 3053 (w), 2939 (m, CH), 2849 (w), 1745 (s,
=
2.3. Computational details
Crystal Explorer 3.1 program [26] was used to perform the Hir-
shfeld surface analysis. The intermolecular interactions in the crys-
tal structure C1 are located and quantified using the dnorm map
and the 2D fingerprint (FP) plots, respectively [].
C
C), 1606 (m), 1493 (m), 1371 (w), 1335 (m), 1286 (s), 1209 (w),
=
1145 (s, P O), 1070 (s), 1028 (w), 953 (s, P-N), 847 (w), 793 (w),
735 (s, P-N), 692 (m), 615 (w), 544 (w, Sn-C), 502 (w), 455 (s), 449
(m, Sn-O). UV–Vis in ethanol: λmax = 229 nm (π→π∗), 280 nm
(n→π∗).
The X-ray structures were used as starting points for DFT cal-
culations in the gas phase using the Gaussian 09 suite of programs
[27]. Since X-ray crystallography cannot locate accurately the po-
sition of the hydrogen atoms, optimization of the hydrogen atoms
positions is needed for the X-ray structures. The structures (L1-L3;
C1-C3) were fully optimized using B3LYP [28]. Non-metal atoms
H, C, N, O, P and Cl were described by the standard basis set 6–
311+G∗, but LanL2DZ [29] was used for Sn atom. Quantum the-
ory of atoms in molecules (QTAIM) [30], and natural bond orbital
(NBO) [31] analyses were performed at the B3LYP/LANL2DZ/6–
311+G∗ level of theory to evaluate the electronic structure of these
molecules. The HOMO - LUMO energies and related parameters
such as electronegativity, chemical hardness and softness for the
selected compounds were calculated at the title level.
2.4.4. Preparation of SnP2O7 nanomaterial
To fabricate tin pyrophosphate nano-structures, the 0.073 g of
tin(IV)-phosphoric triamide complex at two different sizes, C1 and
C1a, was calcinated at 760°C in a furnace in air and without any
surfactant for 4 h. The SnP2O7 nanomaterials were obtained at this
thermal treating.
3. Results and discussion
Scheme 1 shows the reaction between triphenyltinchloride and
N-phenyl-N,N´-bis(pentamethylene) phosphoric triamide (L1) by
´
´
two different methods and their conversion to nano-structured tin
pyrophosphate by calcination at 760°C. The reaction between lig-
and (L1) and SnPh3Cl provided a crystalline material of the for-
mula Sn(Ph)3Cl[C6H5NHP(O)(NC5H10)2] (C1). The IR spectra indi-
2.4. Synthesis
2.4.1. Synthesis of N-phenyl-N,N´-bis(pentamethylene) phosphoric
´
´
=
triamide (L1)
cate that the ʋ(P O) value decreases from L1 (1165 cm−1) to C1
=
The ligand (L1) was prepared and purified according to the lit-
erature procedure [23]. To a stirred solution of N-phenyl phospho-
ramidic dichloride (1 mmol, 0.209 g) in dry acetonitrile, piperidine
(1145 cm−1), exhibiting the weakening of the P O bond. Also, the
ʋ(P-N) increases from 926 cm−1 (in L1) to 955 cm−1 (in C1) that is
due to the enhanced interaction of phosphorus atom with nitrogen
lone pair to form a stronger, partial multiple bond. Other promi-
nent band at 3157 cm−1 is assigned to N-H vibrational mode that
shifts toward higher frequencies in the coordinated ligand (3269
(4 mmol, 0.341 g) was added dropwise at 0 C and the mixture
º
stirred for 5 h. Then the solution was evaporated and the result-
ing white precipitate was washed with distilled water.
M.p. 129–130°C. IR (KBr, cm−1): 3157 (m, NH), 3051 (w), 2931
cm-1). Whereas the N H bond participates in the hydrogen bond-
–
=
–
(m, CH), 2845 (w), 1745 (s, C C), 1601 (m), 1497 (s), 1448 (m),
ing, the positive shift of υ(N H) may be attributed to the weaken-
˚
=
1413 (m), 1335 (m), 1288 (m), 1213 (s), 1165 (s, P O), 1119 (m),
ing of the hydrogen bond from NH…OP=O (dN…O = 3.000 A) in L1
3

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Fig. 1. The ORTEP diagram of C1. Ellipsoids are drawn at the 50% probability level.
˚
gles are nearly tetrahedral that range from 107.9(3) to 116.45(13) ,
º
º
[23] to NH…Cl (dN…Cl = 3.451 A) in C1, which was confirmed by
while P-N(aniline)-C bond angles are deviate slightly from the ideal-
the X-ray crystallographic structures.
ized value, 120 , range from 118.6(2) to 128.8(2) . The presence of
º
º
º
In order to check prevailing coordination modes, various mo-
lar ratios of ligand to SnPh3Cl were assessed in the crystalliza-
tion. The crystals of the five-coordinated complex C1 grew from
a sample of 2:1 ligand-to-Ph3SnCl ratio, therefore, we may guess
that the formation of C1 is rather driven by the steric and elec-
tronic features of the ligand L1, and is independent of the mo-
lar ratio. Selected spectroscopic data of C1 are listed in Table S1.
The ORTEP view of C1 is represented in Fig. 1 as well. The co-
ordination polyhedron of tin can be described as distorted trig-
onal bipyramidal, with three phenyl groups [Sn(1)-C(9), 2.124(2);
Sn-Cl group in complex C1 leads to the formation of intermolec-
ular N(35)H(35)…Cl2 classical hydrogen bonds, which build up 1D
chains of tin(IV) adducts and the free ligand expanding along [100]
direction (Fig. 2a). The presence of short contacts as H…H and
C…H results in a 2D network (Fig. 2b).
We used the Hirshfeld surface analysis to explore the inter-
molecular interactions [37] in a molecular crystal of C1. The Hirsh-
feld surfaces mapped with the normalized contact distance, dnorm
˚
,
range −1.0 to 1.0 A, and full fingerprint plots were generated by
means of the program Crystal Explorer 3.0 [38]. dnorm is displayed
using a red-white-blue color scheme, and its value is negative
(red regions) and positive (blue regions) for contacts shorter and
longer than van der Waals separations, respectively. Fingerprint
plots, constructed by plotting de against di (de and di are defined
as distances from the surface to the nearest nucleus exterior and
interior to the surface, respectively) simultaneously summarize the
information from the intermolecular interactions present in molec-
ular crystals into a two-dimensional colored plot. On the Hirshfeld
surfaces (dnorm) of C1 (Fig. 3a), one deep red area and one light red
˚
Sn(1)-C(3), 2.135(2) and Sn(1)-C(15), 2.137(2) A] in the equato-
˚
rial plane, chloro atom (Sn(1)-Cl(2), 2.550(6) A) and the phos-
˚
phoryl oxygen atom (Sn(1)-O(21), 2.297(14) A) at the axial sites.
The trans angle around tin, Cl2-Sn1-O21, is 177.59(4) , so it de-
º
viates only slightly from linearity, and the sum of angles in the
trigonal girdle around Sn are 359.4 . The Sn-C and Sn-Cl bond
º
lengths are in the range of the covalent bond [32], while the Sn-
=
O bond length is typical for the coordinate bond [33]. The P
˚
O
bond length in molecule C1 is 1.486 (15) A that is larger than the
˚
=
normal P O bond length (1.45 A) [34]. The P atom has slightly
–
spot, labeled as 1 and 2, display the intermolecular N H…Cl in-
distorted tetrahedral configuration, with the surrounding angles
–
–
teractions as well as C H…H C weak interaction, respectively. On
around the P atoms in the range of 106.80(10) - 112.73(9) . The
º
˚
˚
–
the two-dimensional fingerprint plots of C1, the N H…Cl contacts
P-N bonds (1.645(2)−1.654(3)A in L1 and 1.626(19)−1.646(18)A in
˚
appear as two long sharp spikes, comprising 9.1% of the total Hir-
shfeld surface area of the molecule (Fig. 3b, top-right). The upper
spike (where de>di) corresponds to the hydrogen-bond donor (la-
beled as 1a), and the lower spike (where de<di) corresponds to the
C1) are shorter than the typical P-N single bond length (1.77 A)
[34]. Selected structural data for C1, similar complexes contain-
=
ing (C6H5)3(Cl)Sn-O P- moiety [[35], [36]] and their corresponding
phosphoramides (L1 - L3) (Scheme 2) are presented in Table 1. It
˚
hydrogen-bond acceptor (labeled as 1b), with de+di ~ 2.4 A. More-
=
is seen from the table that the Sn-O, P O, and P-N bond lengths
˚
˚
over, the proportion of H…H and C…H short contacts is quantified
as 72.6% and 18.3%, respectively (Fig. 3b, bottom-right and bottom-
are in the range of 2.297(14)−2.464(15)A, 1.483(18)−1.489(15)A
˚
and 1.626(19)−1.686(7)A, respectively. The O-P-N(aniline) bond an-
4

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
(C6H5)3SnClL1
L1= (C6H5NH)P(O)(NC5H10)2
(C6H5)3SnCl
L2= (4-NO2C6H4NH)P(O)(NC4H8O)2
L3= (C6H5)2P(O)(NHC5H4N)
(C6H5)3SnClL3
(C6H5)3SnClL2
Scheme 2. The structure of some complexes containing moiety (C6H5)3SnCl and their corresponding ligands.
Table 1
Selected structural data for compounds L1, L2, C1-C3.
Crystal system,
=
–
–
– –
P N C
Compound
L1
Space group
Sn-O
-
P
O
P-N
O
P
N
Ref
Triclinic, P¯ı
1.486(2)
1.644(3)
116.45(13)
128.8(2)
[22]
1.644(2) 1.654(3) 110.94(12)
109.79(12)
124.7(2),
118.6(2)
118.6(2),
119.0(2)
L2
Monoclinic,
P21/n
-
1.476(11)
1.486(15)
1.483(18)
1.489(15)
1.657(12)
1.638(12)
1.647(12)
113.49(6)
111.52(6)
111.14(6)
127.27(10)
120.00(9),
125.69(9)
117.95(10,
122.17(9)
128.63(15)
122.27(16),
121.79(16)
125.54(16),
119.01(16)
127.95(19)
126.5(7),
[35]
Triclinic, P¯ı
2.297(14)
2.313(14)
2.464(15)
1.646(18)
1.626(19)
1.634(19)
112.73(9)
110.51(9)
110.46(9)
This work
[Sn(C6H5)3ClL1]
(C1)
Monoclinic,
P21/n
1.651(2)
1.686(7)
1.635(14)
113.22(9)
107.9(3)
111.9(6)
[35]
[Sn(C6H5)3ClL2]
(C2)
120.2(6)
125.6(12),
119.3(11)
124.93(15)
Monoclinic,
C2/c
1.666(18)
114.26(9)
[36]
[Sn(C6H5)3ClL3]
(C3)
–
L1: (C6H5NH)P(O)(NC5H10 )2; L2: (4 NO2C6H4NH)P(O)(NC4H4O)2; L3: (C6H5)2P(O)(NHC5H4N).
left). This analysis shows the major influence of the H…H short
contacts in the 2D network.
Figure S1 shows the UV–Vis spectrum of the tin(IV) complexes
(C1 and C1a) dissolved in ethanol. The absorption bands in the
UV region are observed at wavelengths of about 229 and 280 nm,
which can be attributed to the interligand π → π∗ and n → π∗
transitions [[21], [39]]. It is clearly seen that the UV–Vis spectrum
of the complex is very similar for both scales.
Spectral
studies
of
nanostrawberry
[N-phenyl-
N,
´
N´-bis(pentamethylene) phosphoric triamide] chloro triph-
´
enyltin (IV)
The elemental analysis, IR and UV–Vis spectra of the nanostruc-
ture (denoted by C1a) and of the single crystalline material are
indistinguishable. The medium IR absorption bands around 3269–
Fig. 5 shows the simulated XRD pattern from single crystal X-
ray data of compound C1 compared to the XRD pattern of a typ-
ical sample of C1 and C1a prepared by the evaporation process
and sonochemical method, respectively. Acceptable matches, with
slight differences in 2Ɵ, were observed between the simulated
and the experimental powder X-ray diffraction patterns (Fig. 5a-
c), which indicate the same single crystalline phases for the com-
pound obtained by both two methods. The formation of materials
with small size could only happen when the concentration of ini-
tial reagents is within a suitable range for nucleation. The mor-
3263 cm−1 are assigned to N H modes and the C H modes involv-
ing the aliphatic ring hydrogen atoms produce a band at around
2940 cm−1 (Fig. 4). The absorption band near 1493 cm-1 corre-
sponds to ring vibrations of the phenyl moiety, and vibrations of
the phosphoryl group are observed around 1145 cm−1. The band at
about 544 cm−1 corresponds to stretching frequency of Sn-C bonds
as well as the medium band at 449 cm−1 is assigned to the Sn-O
stretching mode.
–
–
5

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Fig. 2. (a) Representation of dimeric units in C1 and the association of them through NHꢀCl interactions, creating 1D chains along [100] direction; (b) Side view of the
crystal packing, which show connection of 1D chains through short contacts H…H and C…H in 2D network.
Table 2
Calculated natural charges, second order stabilization energies between donor and acceptor orbitals (E(2), kcal/mol), natural electron configuration (NEC),
=
hybridization of O lone pairs in P = O bond, and Wiberg bond indices of Sn-O and P O in the studied molecules.
Atomic
Charge
NEC
Hybridization
WBI
E(2)
-
OP=O
O in P
O
LP of (O)
Sn-O
=
=
P O
Compound
L1
q(Sn)
-
q(OP=O
)
−1.09
[Core]2S1.802p5.28
SP2.28d0.05
LP(1) SP0.5 LP(2) SP1.00
LP(3) SP1.00
1
L2
-
−1.08
−1.07
−1.14
-
[Core]2S1.802p5.27
[Core]2S1.802p5.25
[Core]2S1.772p5.36
SP1.8
LP(1) SP0.55 LP(2) SP1.00
LP(3) SP1.00
LP(1) SP0.51 LP(2) SP1.00
LP(3) SP0.99d0.70
LP(1) SP0.63 LP(2)
SP99.99d0.11 LP(3)
SP0.99d0.52
L3
-
-
SP1.87
SP1.61
[Sn(C6H5)3ClL1] (C1)
2.170
29.50
0.1431 1.0848
[Sn(C6H5)3ClL2] (C2)
[Sn(C6H5)3ClL3] (C3)
2.158
2.091
−1.12
−1.13
24.77
26.28
[Core] 2S1.772p5.34
SP1.66
SP1.87
LP(1) SP0.61 LP(2)
SP99.99d0.61 LP(3) SP1.00
LP(1)SP0.59
LP(2)SP99.99d0.07
LP(3)SP87.1d0.04
0.1154 1.1266
0.1409 1.0810
[Core]2S1.762p5.363p0.01
6

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Fig. 3. Hirshfeld surfaces mapped with (a) dnorm of C1 and (b) 2D fingerprint plots, full and resolved into HCl/ClH, CH/HC and H/H contacts showing percentages of contacts
contributed to the total Hirshfeld surface area of molecule.
phology and size of C1a, for two samples which were prepared
by the sonochemical process, were investigated by means of scan-
ning electron microscopy (SEM). As could be observed, concentra-
tion decrease from 0.01 mM (Fig. 6a) to 0.007 mM (Fig. 6b) results
in the formation of the smaller nano-structure. In our previous pa-
pers, we reported triorganotin-phosphoramides with a rod mor-
phology at nano and micro scale [[21,39]]. Here, the morphology of
C1a prepared by the sonochemical method is very interesting. It is
composed of rods with diameters between 50 and 70 nm and the
length varying between 188 and 360 nm, so arranged as to form
a strawberry network (Fig. 6b). Additionally, the chemical purity
and stoichiometry of C1a were verified by EDX analysis. The EDX
spectra in Fig. S2(a) confirm the presence of C, N, O, P, Cl, and Sn
elements in the nano-structured of C1a with weight percentages
of 57.37%, 18.33%, 21.72%, 1.23%, 0.79%, and 0.56%, respectively. The
elemental mapping of nano powders C1a is presented in Fig. S2(b).
In these images, the uniform distribution of the elements was ob-
served throughout the sample, which confirmed the formation of
tin-phosphoric triamide NPs (C1a).
7

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Fig. 4. IR spectra of (a) bulk material of C1 and (b) nano-structure of C1a.
calcinated at 760°C in air and without any surfactant or capping
molecule. The final product obtained upon calcinations of the title
compound is, based on their XRD patterns, cubic SnP2O7, in per-
fect agreement with the results of EDS (Table S2). The phase purity
of the prepared cubic SnP2O7 nano-powders is completely obvious
and all diffraction peaks are perfectly indexed to the cubic SnP2O7
˚
structure with the cell parameters of a = b = c = 7.95 A, α=β=γ =
90 , Z = 4 and S.G = Pa3 (JCPDS card file No. 03–0287). No char-
º
acteristic peaks of impurities are detected in the XRD pattern (Fig.
S3). The SEM image and the corresponding particle size distribu-
tion histogram of the residue obtained from the calcination of C1
and C1a at 760°C under air atmosphere show that the particles are
spherical, but ranging from 20 to 60 nm in size with the frequency
of 30–40 nm at diameter for C1a (Fig. 8a, b).
3.1. Quantum chemical calculations
The optimized structures of the complex C1 were obtained at
the B3LYP and cam-B3LYP methods with LANL2DZ/6–311G∗ level
basis set. Similar geometric parameters are obtained by the two
applied methods, some of the calculated bond lengths and bond
angles are included in Table S3. Although the biggest differences
between calculated and experimental values of bond lengths and
Fig. 5. The XRD patterns of (a) simulated from single crystal X-ray data of complex
C1; (b) single crystal of C1 and (c) nano-structure of C1a.
The thermogravimetry and differential thermal analysis (TGA
and DTA) were carried out in flowing nitrogen at the heating rate
˚
˚
angles are about 0.080 A, 0.063 A and 4.77°, 6.66° for B3LYP
and cam-B3LYP methods, respectively, the results obtained by
the B3LYP method at 6–311G∗∗/LANL2DZ correlate slightly bet-
ter for C1. Subsequently, NBO, QTAIM, and Wiberg index analyses
were performed to obtain more information about bonding and
electronic aspects for the new synthesized complex, similar tri-
organotins(IV) and the corresponding ligands. By QM calculations,
HOMO-LUMO energy gap was calculated as well.
of 10 C/min (Fig. 7a). The thermogram of the nano-structures C1a
º
indicates that the complex is thermally stable up to nearly 195 C.
º
Decomposition of C1a occurs between 195 and 273 C in one step
º
with a mass loss of 70% (calc. 74.1%) so that the organic segments
including phenyl, pentamethylene rings as well as aniline and chlo-
rine groups are eliminated in the same decomposition step. The
result suggests that there is no coordination water in the complex.
Also, the DTA curve shows an endothermic peak at 203 C corre-
º
sponding to a sharp weight loss in the TG curve; it proves that the
complex undergoes decomposition.
3.2. NBO analysis
The use of organotinphosphoric triamides as precursors for
preparing tin pyrophosphate nano-materials has not yet been in-
vestigated thoroughly; hence, based on our knowledge, these com-
pounds were synthesized by calcination of nano-tin phospho-
ramide complexes in our laboratory for the first time [39]. It seems
that the kind of precursor can change the morphology, size and
type of SnP2O7 phase. Then, bulk form (C1) and nanoscale (C1a)
The electronic data of some triorganotin(IV) complexes (C1 -
=
C3) all containing (C6H5)3ClSn-O P moiety and their correspond-
ing phosphoramides (L1 - L3) are presented in Table 2. In the
phosphoramide L1, the negative charge localized on OP=O atom
is larger in magnitude due to the nature of the substituents on
phosphoryl, and the hybridization of occupied orbitals by the lone
8

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Fig. 6. SEM photograph of nanostructures C1a prepared by ultrasonic frequency 80 Hz at concentrations of initial reagents [Sn(IV)]/[L] = 0.01 mM (a) and 0.007 mM (b).
ization energies, E(2), for the electronic delocalization LP(OP=O) to
LP∗(Sn) (LP∗ = empty valence orbital), can be used to characterize
the strength of the donor-acceptor coordination interactions. Based
on the results in Table 2 for the coordination bond in the complex
C1 containing PhNH and pentamethylene substituents, the higher
stabilizing energy of 29.5 kcal•mol−1 indicates the stronger Sn-O
interaction than in the other complexes (E(2): 24.77 (C2) and 26.28
(C3) kcal•mol−1). Another factor in probing the bond strength is
the Wiberg bond index. Table 2 shows the selected bond indexes
for the complexes. In C1, the calculated Wiberg bond order for Sn-
O bond is larger than those found for C2 and C3, which demon-
strates the stronger donor-acceptor interaction between the central
metal and the O atom of the phosphoric triamide moiety.
pair of this atom, LP(OP=O), takes more a p-character. The elec-
tronic charge is transferred from the neighbors to the O atom as
a result of the polarization effect. This electronic redistribution
occurs even more when the ligands are coordinated to SnPh3Cl,
as the polarization effect arises from the electrostatic field of the
Sn(IV) atom [40]. For example, the natural electronic configuration
(NEC) of the OP=O atom is [core] 2s1.80 2p5.28 in the free ligand
(L1), which changes nearly to [core] 2s1.77 2p5.36 by coordinating
to the tin in Sn(C6H5)3ClL1. Similarly, the electronic population of
2p orbital of the oxygen increases for the other ligand - complex
pairs in Table 2. The hybridization of occupied orbitals by the lone
pair of the mentioned atom, as expected, is affected upon com-
plexation. Furthermore, the atomic charges of donor sites become
more negative when the ligand is coordinated. Electron delocal-
9

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Fig. 7. (a) Thermal behavior (TGA/DTA) and (b) DSC curve of nanostructures C1a.
Fig. 8. SEM photograph and the corresponding particle size distribution histogram of SnP2O7 nano-particles prepared by calcination of (a) bulk-form C1 and nano-scale C1a
(b). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
10

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
Fig. 9. Plots of the HOMO, LUMO orbitals of the compounds L1-L3 and C1-C3, and ࢞E (The energy gap between HOMO and LUMO) (eV).
Table 3
Calculated QTAIM parameters (electron density, ρ, its Laplacian, ∇^2 ρ, and total electronic energy density, H(r)) at selected critical points.
=
Sn…O
P
O
Comp.
2
2
H(r)
G(r)
V(r)
∇ ρ
P
H(r)
G(r)
V(r)
∇ ρ
ρ
-
-
-
-
-
−0.6134
−0.6201
−0.5950
−0.5443
−0.5556
−0.5252
0.5255
0.5311
0.5098
0.4736
0.4845
0.4556
−1.1389
−1.1512
−1.1048
−1.0179
−1.0400
−0.9808
−0.3514
−0.3559
−0.3408
−0.2829
−0.2844
−0.2784
0.2309
0.2321
0.2265
0.2246
0.2299
0.2167
L1
-
-
-
-
-
L2
-
-
-
-
-
L3
−0.1510
−0.1498
−0.1436
0.1608
0.1528
0.15495
−0.3118
−0.3026
−0.2986
0.0390
0.0128
0.0453
0.1921
0.1756
0.1899
[Sn(C6H5)3ClL1] (C1)
[Sn(C6H5)3ClL2] (C2)
[Sn(C6H5)3ClL3] (C3)
3.3. Topological analysis of electron density
+0.045 au, which characteristic the predominantly closed-shell in-
teractions [30]. Despite falling in a region of charge depletion with
2
The calculated values of the electron density (ρ), its Lapla-
∇ ρ>0, the negative values of H(r) suggest that the interactions
2
cian (∇ ρ), and electronic energy density H(r) at the bond critical
are principally electrostatic in nature with an amount of tin-ligand
2
=
points (BCP) of P O and Sn-L paths are listed in Table 3. The ρ
covalent interaction. The related ρ and ∇ ρ are larger as the inter-
=
values at the P O BCPs are in the range of 0.217–0.232 au and the
action becomes stronger. The trend observed for the Sn-L bonding
strength in complexes is in agreement with NBO analysis.
2
corresponding ∇ ρ values are all negative, ranging from −0.278
=
to −0.356 au Based on the obtained BCPs for P O in all selected
2
3.4. HOMO and LUMO
molecules (∇ ρ<0 and H(r)<0), this bond is the stronger covalent
bond in ligand L2 and its corresponding complex C2 than in other
ligands and complexes (Table 3). Moreover, the electron density (ρ)
values at the Sn-L BCPs are in the range of 0.176–0.192 au and the
The energies of the highest occupied molecular orbital (HOMO)
and the lowest unoccupied molecular orbital (LUMO) were com-
puted using a DFT approach [41]. The energy gap, ࢞E (࢞E = ELUMO
2
corresponding ∇ ρ values are all positive, ranging from +0.013 to
11

M. Alipour, N. Dorosti and M. Kubicki
Journal of Molecular Structure 1230 (2021) 129630
- EHOMO), is an important parameter to measure the reactivities of
selected molecules (L1 - L3; C1 - C3). Fig. 9 shows the energy gap
and isodensity surface plot of HOMO and LUMO for ligands (L1
- L3) and the corresponding triorganotin(IV) complexes (C1 - C3).
The ࢞E values infer that triorganotin(IV) C2 has high chemical ac-
tivity, low kinetic stability and high softness value [42]. As can be
seen, the LUMO electrons are mainly delocalized over the phenyl
rings for all molecules, except phosphoramide L2 with delocaliza-
tion on nitroaniline moiety. For the most compounds, the HOMO
electrons are delocalized over moieties containing nitrogen atom
as morpholine, pyridine, and amine rings, as well as Cl atom in
two triorganotin(IV) C1, C3 only. Using HOMO and LUMO energies,
ionization potential (IP) and electron affinity (EA) can be estimated
as IP ~ -EHOMO, EA ~ -ELUMO [43]. The chemical hardness (ƞ) = (IP-
EA)/2 [44], electronegativity (x) = (IP + EA)/2 [45], chemical poten-
tial (μ) = (IP + EA)/2 and chemical softness (S) = 1/2ƞ [46] values
were calculated and were presented in Table S3. According to the
information of Table S4, the complex C1 shows a higher amount
of gap energy and hardness (ƞ), while the C2 is softer than other
two complexes. The variation of x values is supported by the elec-
trostatic potential. For the selected molecules, electron will be par-
tially transferred from the one of low x to that of high x (elec-
trons flow from high chemical potential to low chemical potential).
These observations can be explained by attention to the substitu-
tions of the P(O) group.
Supplementary data
CCDC 1871142 contains the supplementary crystallographic
data for C34H41ClN3OPSn. The data can be obtained free of
charge from the Cambridge Crystallographic Data Centre via fax:
+441223336033; E-mail: deposit@ccdc.cam.ac.uk or www.ccdc.
cam.ac.uk.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper
Acknowledgment
Financial support of this work by Lorestan University is grate-
fully acknowledged.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.molstruc.2020.129630.
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