Structures of a novel phosphoric triamide and its organotin(IV) complex

Article abstract of DOI:10.1016/j.jorganchem.2013.08.003

A new phosphoric triamide 4-NO₂C₆H ₄NHP(O)(NC₄H₈O)₂ (1) and its organotin(IV) complex SnCl(C₆H₅)₃[4-NO ₂C₆H₄NHP(O)(NC₄H₈O) ₂] (2) were synthesized and characterized by ³¹P, ¹H, ¹³C NMR, IR spectroscopy and elemental analysis. The crystal structures of compounds 1 and 2 were determined by X-ray crystallography. Both compounds crystallize in monoclinic crystal system with P2₁/n space group. The structure of 1 contains two symmetrically independent molecules while for 2 only one independent molecule is present with a five-coordinated tin(IV) in a distorted trigonal bipyramidal configuration. Strong intermolecular N-Ha?O and N-Ha?Cl hydrogen bonds together with weak intermolecular C-Ha?O hydrogen bonds connect molecules of 1 and 2 into 3D networks. Both compounds were also prepared as nanoparticles of the size 15-20 nm and a spherical morphology, as confirmed by SEM micrographs.

Full text of DOI:10.1016/j.jorganchem.2013.08.003

Journal of Organometallic Chemistry 745-746 (2013) 432e438
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Structures of a novel phosphoric triamide and its organotin(IV)
complex
,
a
b
Zahra Shariatinia a , Hourieh Sadat Mirhosseini Mousavi , Pablo J. Bereciartua ,
*
Michal Dusek b
a Department of Chemistry, Amirkabir University of Technology (Polytechnic), P.O. Box 15875-4413, Tehran, Iran
b Institute of Physics of the ASCR, v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic
a r t i c l e i n f o
a b s t r a c t
Article history:
A
new phosphoric triamide 4-NO2C6H4NHP(O)(NC4H8O)2 (1) and its organotin(IV) complex
SnCl(C6H5)3[4-NO2C6H4NHP(O)(NC4H8O)2] (2) were synthesized and characterized by 31P, 1H, 13C NMR, IR
spectroscopy and elemental analysis. The crystal structures of compounds 1 and 2 were determined by
X-ray crystallography. Both compounds crystallize in monoclinic crystal system with P21/n space group.
The structure of 1 contains two symmetrically independent molecules while for 2 only one independent
molecule is present with a five-coordinated tin(IV) in a distorted trigonal bipyramidal configuration.
Strong intermolecular NeH/O and NeH/Cl hydrogen bonds together with weak intermolecular C
eH/O hydrogen bonds connect molecules of 1 and 2 into 3D networks. Both compounds were also
prepared as nanoparticles of the size 15e20 nm and a spherical morphology, as confirmed by SEM
micrographs.
Received 17 June 2013
Received in revised form
20 July 2013
Accepted 4 August 2013
Keywords:
Organotin(IV) complex
Phosphoric triamide
X-ray crystallography
Hydrogen bond
Nanoparticles
Ó 2013 Elsevier B.V. All rights reserved.
NMR
1. Introduction
In this work, a new phosphoric triamide (1) as well as a novel
organotin(IV) complex (2) were synthesized and characterized by
Phosphoramide derivatives belong to a famous drugs family
showing prominent anti-HIV [1], anti-HCV [2,3], antibacterial [4],
antitumor and anticancer activities [5,6] as well as they act as
enzyme inhibitors [7]. They are also efficient catalysts in chemical
reactions [8,9]. The crystal structures of some phosphoramide
molecules with two [10e12] and four [13,14] independent mole-
cules in the crystal packing and an organotin(IV) complex [15]
including two independent molecules were reported. The organo-
tin(IV) complexes as are known for their important applications as
antibacterial and anticancer [16e18], antifungal agents [19,20], as
well as catalysts [21]. It should also be noted that most of the
organotin(IV) complexes with phosphoramide ligands are six co-
ordinated [14,15,22] and a few are five coordinated [23]. Recently,
the preparation of nanosized compounds has become of great in-
terest due to the prominent properties at this scale including large
specific surface areas and enhanced optical [24], electrical [25,26]
and medical performance [27,28]. The nanoparticles of some
organotin(IV) complexes of phosphoramides have been synthe-
sized using ultrasonic method [29].
1H, 13C, 31P NMR, IR spectroscopy and elemental analysis. Also, the
structures of compounds 1 and 2 were determined by X-ray crys-
tallography. Using ultrasonic method, the nanoparticles of com-
pounds 1 and 2 were prepared and investigated by SEM and XRD
analyses. Comparing the structures 1 and 2 with those of reported
phosphoramides (including nitrophenyl moiety in their structures)
that have indicated potential therapeutical anticancer and enzyme-
inhibitor properties [4,30,31] and with organotin(IV) complexes of
phosphoramides possessing antibacterial activities [23], it can be
expected that our new compounds will show desirable pharma-
ceutical applications.
2. Experimental
2.1. Instrumentation
The 1H, 13C, 31P and 119Sn spectra were recorded on a Bruker
Avance DRS 500 spectrometer. 1H and 13C chemical shifts were
determined relative to internal Si(CH3)4 and 31P chemical shifts
relative to 85% H3PO4 as external standard. Infrared (IR) spectra
were recorded on a Shimadzu model IR-60 spectrometer. Elemental
analysis was performed using a Heraeus CHN-O-RAPID apparatus.
Melting points were obtained with an Electrothermal instrument.
* Corresponding author. Tel.: þ98 2164542766; fax: þ98 2164542762.
E-mail addresses: shariati@aut.ac.ir, shariatiz@yahoo.com (Z. Shariatinia).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.08.003

Z. Shariatinia et al. / Journal of Organometallic Chemistry 745-746 (2013) 432e438
433
O
P
H
N
O2N
Cl
+
4
N
H
Cl
O
NO2
O
P
O2N
C6H5
Sn
HN
P
SnCl(C6H5)3
2
N
N
H
Cl
O
N
O
O
N
C6H5
C6H5
N
O
O
(1)
(2)
Scheme 1. The synthesis pathway of compounds 1 and 2.
Table 1
Selected spectroscopic NMR and IR data of compounds A, 1 and 2.
Compound
d(
31P) (ppm)
2J(PNH) (Hz)
3J(P,C) (Hz)
n
(P]O) (cmꢀ1
)
n
(PeN) (cmꢀ1
)
n
(NH) (cmꢀ1
)
4-NO2C6H4NHP(O)Cl2 (A)
1
2
6.34
9.99
10.30
10.6
e
9.0
1249
1196
1169
942
1104, 964
1111, 971
3400
3425
3445
7.0 (aromatic), 5.7 (aliphatic)
6.6 (aromatic), 5.4 (aliphatic)
e
ꢀ
The scanning electron microscopy (SEM) micrographs were ob-
tained from Philips instrument (XL30), under vacuum, accelerated
at 20 KV. The ultrasonic bath (Sono Swiss, model SW 12H with 50/
60 Hz frequency, 1000 W power and 220e240 V voltage) was used
for the synthesis of nanoparticles.
radiation (
l
¼ 1.5418 A). The data processing including the empirical
absorption correction by spherical harmonics was done with Cry-
salis Pro [32]. Structures were solved by the charge flipping algo-
rithm of Superflip [33] and refined by Jana2006 [34]. The H-atom
parameters for both structures were derived from the parent carbon
atoms. For 1 we found two symmetry independent molecules while
in the case of 2 only one symmetry independent molecule exists. For
2 the disordered C4H8ON morpholinyl rings were described by a
rigid body in four positions. It should be noted that the disorder in 2
could not be avoided by lowering of the symmetry.
2.2. X-ray structure analysis
X-ray data of compounds 1 and 2 were collected at 120 K on a
single crystal diffractometer Gemini with mirrors-collimated Cu K
a
Table 2
Crystallographic data for compounds 1 and 2.
Compound
1
2
Chemical formula
Mr
C28H42N8O10P2
712.6
C32H36ClN4O5PSn
741.8
Crystal system, space group
Temperature (K)
Monoclinic, P21/n
121
9.5609 (2), 10.6061 (3), 33.5907 (11)
96.663 (2)
3383.22 (16)
4
Monoclinic, P21/n
120
8.9123 (2), 37.5953 (6), 10.2917 (2)
107.196 (2)
3294.20 (12)
4
ꢀ
a, b, c (A)
b
(ꢁ)
3
ꢀ
V (A )
Z
Radiation type
m
Cu K
1.74
a
Cu K
7.75
a
(mmꢀ1
)
Crystal size (mm)
Diffractometer
Absorption correction
Tmin, Tmax
0.27 ꢂ 0.13 ꢂ 0.12
0.35 ꢂ 0.27 ꢂ 0.16
Xcalibur, Atlas, Gemini ultra diffractometer
Multi-scan, CrysAlis PRO, Agilent Technologies
0.935, 1
Xcalibur, Atlas, Gemini ultra diffractometer
Multi-scan, CrysAlis PRO, Agilent Technologies
0.455, 1
No. of measured, independent
19,355, 5948, 5075
54,522, 5830, 5344
and observed [I > 3
s(I)]
reflections
Rint
(sin
R[F2 > 3
0.022
0.597
0.031, 0.045, 1.50
0.054
0.598
0.025, 0.070, 1.25
ꢀꢀ1
(A
q
/
l
)
)
max
s
(F2)], wR(F2), S
No. of reflections
No. of parameters
No. of restraints
H-atom treatment
5948
439
1
Constrained
0.21, ꢀ0.29
5830
366
1
Constrained
0.35, ꢀ0.43
ꢀꢀ3
Drmin (e A )
Drmax
,

434
Z. Shariatinia et al. / Journal of Organometallic Chemistry 745-746 (2013) 432e438
Table 3
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) for compounds 1 and 2.
1
2
P1eO1
P1eN2
P1eN4
P1eN5
P2eO2
P2eN1
P2eN3
P2eN6
O3eC6
O3eC12
N1eC10
1.4759 (11)
1.6383 (12)
1.6569 (12)
1.6469 (12)
1.4761 (11)
1.6451 (12)
1.6580 (12)
1.6341 (12)
1.4323 (18)
1.4307 (19)
1.4764 (18)
Sn1eCl1
Sn1eC2
Sn1eC6
Cl1eN1i
P1eO1
2.5340 (6)
2.132 (2)
2.123 (3)
3.289 (2)
1.4828 (18)
1.651 (2)
1.686 (7)
1.635 (14)
1.401 (3)
0.87 (3)
P1eN1
P1eN3a
P1eN3c
N1eC7
N1eH1n1
C2eC16
1.388 (3)
O1eP1eN2
O1eP1eN4
O1eP1eN5
N2eP1eeN4
N2eP1eN5
N4eP1eN5
O2eP2eN1
O2eP2eN3
O2eP2eN6
N1eP2eN3
N1eP2eN6
N3eP2eN6
P2eN1eC10
P2eN1eC16
C10eN1eC16
P1eN2eC4
P1eN2eC15
C4eN2eC15
P2eN3eC21
P2eN3eH1n3
C21eN3eH1n3
C6eO3eC12
111.52 (6)
113.49 (6)
111.14 (6)
105.46 (6)
108.94 (6)
105.95 (6)
110.96 (6)
112.46 (6)
115.54 (6)
107.76 (6)
103.57 (6)
105.89 (6)
118.23 (9)
122.57 (9)
111.78 (11)
120.00 (9)
125.69 (9)
113.00 (11)
128.18 (10)
115.2 (11)
114.9 (12)
110.75 (11)
Cl1eSn1eC1
Cl1eSn1eC2
Cl1eSn1eC6
C1eSn1eC2
C1eSn1eC6
C2eSn1eC6
Sn1eCl1eN1i
O1eP1eN1
O1eP1eN3a
O1eP1eN3c
N1eP1eN3a
N1eP1eN3c
N3aeP1eN3c
Cl1iieN1eP1
Cl1iieN1eC7
Cl1iieN1eH1n1
P1eN1eC7
92.55 (6)
93.82 (6)
92.83 (6)
124.57 (9)
119.49 (8)
115.09 (9)
114.93 (4)
113.22 (9)
107.9 (3)
111.9 (6)
104.9 (3)
107.7 (6)
111.1 (5)
121.38 (9)
110.67 (15)
6.2 (16)
127.95 (19)
115.3 (16)
116.8 (16)
118.49 (16)
123.09 (15)
118.3 (2)
Fig. 1. The ORTEP view of the two independent molecules of compound 1 (50%
probability ellipsoids).
P1eN1eH1n1
C7eN1eH1n1
Sn1eC1eC4
Sn1eC1eC10
C4eC1eC10
2.3. Synthesis
Symmetry code(s): (i) x þ 1, y, z.; (ii) x ꢀ 1, y, z.
d
¼ 3.04 (m, 8H, 4CH2), 3.50 (m, 8H, 4CH2), 7.34 (d, 3J(H,H) ¼ 9.1 Hz,
2.3.1. N-4-Nitrophenyl-N0,N00-bis(morpholinyl) phosphoric triamide
(1)
2H), 8.10 (d, 3J(H,H) ¼ 9.1 Hz, 2H). 13C NMR (d6-DMSO):
¼ 44.72 (s,
d
CH2), 66.87 (d, 3J(P,C) ¼ 5.7 Hz, CH2), 117.63 (d, 3J(P,Cortho) ¼ 7.0 Hz),
To a solution of N-4-nitrophenyl phoramidic dichloride [35]
(10 mmol, 2.55 g) in dry acetonitrile, morpholine (40 mmol,
3.48 g) was added dropwise at 0 ꢁC and the mixture stirred for 24 h.
Then the solution was evaporated and the yellow precipitate was
filtered, washed with distilled water and recrystallized in MeOH/
CH3CN mixture. Yield: 71%. M.p. ¼ 194e195 ꢁC. Anal. calcd. For
125.70 (s), 140.55 (s), 150.45 (s). IR (KBr):
n
¼ 3425 (NH), 2835, 1589
(NO2), 1512, 1485, 1341 (NO2), 1297, 1252, 1196 (P]O), 1104 (PeN),
964 (PeN), 929, 842, 685, 526 cmꢀ1
.
2.3.2. [N-4-Nitrophenyl-N0,N00-bis(morpholinyl) phosphoric
triamide] triphenyl stannate(IV) chloride (2)
C
14H21N4O5P: C, 47.19; H, 5.94; N, 15.72. Found: C, 47.17; H, 5.95; N,
15.71%. 31P NMR (d6-DMSO):
d
¼ 9.99 (m). 1H NMR (d6-DMSO):
To a solution of N-4-nitrophenyl-N0,N00-bis(morpholinyl) phos-
phoric triamide (10 mmol, 3.56 g) in methanol, triphenyltin(IV)
chloride (10 mmol, 3.86 g) was added at room temperature and the
solution was stirred for 72 h. Then the solution was slowly evapo-
rated at RT to yield the single crystals. Yield: 51%. M.p. ¼ 184e
185 ꢁC. Anal. Calc. For C32H36ClN4O5PSn: C, 51.84; H, 4.86; N, 7.55%.
Found: C, 51.82; H, 4.85; N, 7.56%. 31P{1H} NMR (d6-DMSO):
d
¼ 10.30 (s). 1H NMR (d6-DMSO):
d
¼ 3.25 (m, 8H, CH2), 3.66 (m,
8H, CH2), 7.25 (d, 3J(H,H)
¼
9.0 Hz, 2H, AreH), 7.51 (t,
3J(H,H) ¼ 6.4 Hz, 8H, AreH), 7.70e7.77 (m, 7H, AreH), 8.17 (d,
3J(H,H) ¼ 9.0 Hz, 2H, AreH). 13C NMR (d6-DMSO):
d
¼ 44.85 (s),
66.99 (d, 3J(P,C) ¼ 5.4 Hz), 117.14 (d, 3J(P,C) ¼ 6.6 Hz), 125.61 (s),
129.11 (s), 130.42 (s), 136.09 (s), 137.70 (s), 141.75 (s), 147.38 (s). IR
(KBr, cmꢀ1): 3445 (NH), 3226, 3058 (CH), 2967 (CH), 2853, 1598
(NO2), 1511, 1341 (NO2), 1253, 1169 (P]O), 1111 (PeN), 971 (PeN),
927, 850, 732, 692, 457.
3. Results and discussion
3.1. Spectroscopic study
In this study, a new phosphoric triamide 4-NO2C6H4NHP(O)(NC4
Fig. 2. The ORTEP view of compound 2 (50% probability ellipsoids).
H8O)2 (1) and its organotin(IV) complex SnCl(C6H5)3[4-NO2

Z. Shariatinia et al. / Journal of Organometallic Chemistry 745-746 (2013) 432e438
435
Table 4
Selected structural data for compounds 1e7.
Compound
Crystal system, space group
P]O/P]S
PeN(nitroaniline)
OePN(nitroaniline)/SePeN(nitroaniline)
PeN(nitroaniline)eC
Ref
b
4-NO2C6H4NHP(O)
(NC4H8O)2 (1)
Monoclinic, P21/n
1.476 (1), 1.476 (1)
1.657 (1), 1.658 (1)
113.49 (6), 112.46 (6)
127.3 (1), 128.2 (1)
b
SnCl(C6H5)3L2 (2)a
4-NO2C6H4NHP(O)
(OCH3)2 (3)
Monoclinic, P21/n
Orthorhombic, Pbcn
1.483 (2)
1.467 (2)
1.651 (2)
1.639 (2)
113.22 (9)
108.23 (8)
128.0 (2)
128.8 (1)
[40]
4-NO2C6H4NHP(O)
(4-CH3-NC5H9)2 (4)
4-NO2C6H4NHP(O)
(OCH3)2 (5)
4-NO2C6H4NHP(S)
(OCH2CH3)2 (6)
PdCl2L12 (7)c
Monoclinic, P21/c
Orthorhombic, Pbcn
Triclinic, P1
1.479 (1)
1.462 (5)
1.911 (2)
1.972 (2)
1.661 (2)
1.643 (7)
1.654 (3)
1.625 (3)
113.43 (8)
109.4 (4)
110.3 (l)
110.0 (1)
127.4 (1)
129.0 (6)
129.7 (3)
127.5 (2)
[41]
[42]
[43]
[43]
Monoclinic, P21/c
a
4-NO2C6H4NHP(O)(NC4H8O)2 ¼ L.
This work.
b
c
4-NO2C6H4NHP(S)(OCH2CH3)2 ¼ L1.
C6H4NHP(O)(NC4H8O)2] (2) were synthesized (Scheme 1) and
characterized by NMR and IR spectroscopy. A summary of the
spectroscopic parameters of these compounds and A [35] are given
Table 2. Both compounds crystallize in the monoclinic crystal sys-
tem with P21/n space group. Phosphoramide 1 has two symmet-
rically independent molecules (1 and 10) in the crystalline lattice
(Fig. 1). The molecules are significantly different as manifested by
in Table 1. The phosphorus chemical shift,
d(
31P), appears at down
(
31P) is the most down
field from compound A to 1 and 2 so that the
d
fielded in 2 (10.30 ppm). This down field shift shows the most
electron withdrawing of substituents on the phosphorus atom in 2
results in a most deshielded phosphorus atom.
The 1H NMR spectrum of compound
A
reveals 2J(PNH)
coupling constant equal to 10.6 Hz while it disappears in the
spectra of 1 and 2. The 13C NMR spectra indicate that 3J(P,Car-
omatic) coupling constant decreases from 9.0 Hz (in A) to 6.6 Hz
(in 2). Also, 3J(P,Caliphatic) coupling constant for the splitting of
morpholinyl ring carbon atom with phosphorus reduces from
5.7 Hz (in 1) to 5.4 Hz (in 2). The reductions in 3J(P,C) coupling
constants are due to the less interaction of carbon atoms with
phosphorus atoms that are because of changes in electronic and
spatial properties.
The IR spectra indicate that among these compounds, the
n
(P]O) value decreases from A (1249 cmꢀ1) to 2 (1169 cmꢀ1
)
exhibiting the weakening of the P]O bond. The n(PeN) increases
from 942 cmꢀ1 (in A) to 971 cmꢀ1 (in 2) that is due to the
enhanced interaction of phosphorus atom with nitrogen lone
pair to form a stronger partial multiple bond. Also, the NH
stretching frequencies are observed at about 3400 cmꢀ1
.
3.2. X-ray crystallography
Single crystals of compounds 1 and 2 were obtained by slow
evaporation of the solvents at room temperature. The crystallo-
graphic data and the details of the X-ray analysis are presented in
Table 5
The hydrogen bonding data of compounds 1 and 2 (A, ꢁ).
ꢀ
DeH/A (ꢁ)
ꢀ
ꢀ
ꢀ
Compound DeH/A
DeH (A) H/A (A) D/A (A)
1a
N3eH1n3/O1
0.842 (17) 1.910 (17) 2.7490 (16) 174.7 (17)
0.842 (17) 1.947 (17) 2.7850 (16) 174.0 (16)
N4eH1n4/O2ii
C2eH1c2/O4
C3eH1c3/O5
0.96
0.96
2.44
2.45
2.41
2.43
2.44
2.728 (2) 96.77
2.7348 (19) 96.80
2.709 (2) 97.61
2.718 (2) 97.03
3.3895 (18) 172.40
C14eH1c14/O9 0.96
C18eH1c18/O10 0.96
C24eH1c24/O3i 0.96
2b
N1eH1n1/Cl1i
C8eH1c8/O2
C12eH1c12/O3 0.96
0.87 (3)
0.96
2.43 (3)
2.43
2.42
3.289 (2) 172 (2)
2.721 (3) 96.80
2.710 (3) 97.24
Fig. 3. The three-dimensional polymeric chain formed by hydrogen bonds in the
crystal structure of 1. Different colors denote chemical types in (a) and different
molecules in (b).
a
Symmetry code(s): (i) x, y ꢀ 1, z; (ii) x þ 1, y, z.
Symmetry code(s): (i) x ꢀ 1, y, z.
b

436
Z. Shariatinia et al. / Journal of Organometallic Chemistry 745-746 (2013) 432e438
Fig. 4. The three-dimensional polymeric chain formed by hydrogen bonds in the crystal structure of 2.
their torsion angles. For instance, the O1eP1eN4eC19, O2eP2e
N3eC21 and N2eP1eN4eC19, N1eP2eN3eC21 torsion angles are
46.75ꢁ, ꢀ30.69ꢁ and ꢀ75.60ꢁ, ꢀ153.30ꢁ, respectively.
105.46 (6)ꢁ ꢀ 113.49 (6)ꢁ, 103.57 (6)ꢁ ꢀ 115.54 (6)ꢁ and 104.9
(3)ꢁ ꢀ 113.22 (9)ꢁ for molecules 1, 10 and 2, respectively. The PeN
ꢀ
bonds are shorter than the typical PeN single bond length (1.77 A)
The ORTEP view of complex 2 is represented in Fig. 2. In 2, all of
the endocyclic atoms of morpholinyl rings reveal disorder. In the
structure refinement the disorder was sufficiently described by one
morpholinyl ring in a chair conformation which was placed to four
positions. Selected bond lengths and angles of compounds 1 and 2
are given in Table 3. The P]O bond lengths in molecules 1, 10 and 2
[36]. The environments of nitrogen atoms bonded to the morpho-
linyl ring in a chair conformation are deviated from planarity. In
compound 1, the angles P1eN2eC4, P1eN2eC15 and C4eN2eC15
are 120.00 (9)ꢁ, 125.69 (9)ꢁ, 113.00 (11)ꢁ, respectively, with average
119.56ꢁ. Also, the sums of surrounding angles around exocyclic N4
and endocyclic N5 atoms in 1 are 360.06ꢁ and 351.94ꢁ, respectively,
indicating a planar configuration for N4 and a distorted planar
configuration for N5. Analogous observations can be found for the
nitrogen atoms in molecules 10 and 2. The SneC bond lengths in 2
ꢀ
ꢀ
ꢀ
are 1.4759 (11) A,1.4761 (11) A and 1.4828 (18) A that are larger than
ꢀ
the normal P]O bond length (1.45 A) [36]. It is seen that the P]O
bond length is longer in complex 2 relative to those of 1 and 10 that
is due to its weakening upon complexation via phosphoryl oxygen
atom. The central Sn atom in 2 has a distorted trigonal bipyramidal
configuration in which three phenyl rings are placed at equatorial
positions while the Cl atom and phosphoric triamide ligand are in
axial positions (with CleSneO bond angle ¼ 176.16ꢁ).
ꢀ
are 2.132 (2), 2.123 (3) and 2.135 A that are close to those reported
ꢀ
in the literature [37]. The SneCl bond length is 2.5340 (6) A lying
ꢀ
near to the normal covalent radii 2.37e2.60 A [38]. The SneO bond
ꢀ
length is 2.313 A that is shorter than sum of the van der Waals radii
ꢀ
of Sn and O atoms (3.70 A) [39].
The P atoms have slightly distorted tetrahedral configurations
with the surrounding angles around the P atoms in the range of
Selected structural data for compounds 1, 2 and for similar
compounds 3e7 all containing 4-nitroaniline group [40e43] are
Fig. 5. The SEM micrographs of compound 1 with 30k, 60k and 100k magnifications.

Z. Shariatinia et al. / Journal of Organometallic Chemistry 745-746 (2013) 432e438
437
Fig. 6. The SEM micrographs of compound 2 with 30k, 60k and 100k magnifications.
presented in Table 4. It is seen from the table that the P]O, P]S
and PeN(nitroaniline) bond lengths are in the range of 1.462
(5)ꢁ ꢀ 1.483 (2)ꢁ, 1.911 (2)ꢁ ꢀ 1.972 (2)ꢁ and 1.625 (3)ꢁ ꢀ 1.661 (2)ꢁ,
respectively. The OePeN(nitroaniline) and SePeN(nitroaniline) bond
angles are nearly tetrahedral that range from 108.23 (8)ꢁ to 113.49
(6)ꢁ while PeN(nitroaniline)eC bond angles are almost planar and
range from 127.3 (1)ꢁ to 129.7 (3)ꢁ. In all compounds 1e7, the
phosphorus atoms reveal slightly distorted tetrahedral configura-
tions. Also, strong intermolecular NeH/O]P hydrogen bonds are
observed in these structures.
The details about hydrogen bonding of compounds 1 and 2 are
given in Table 5. In compound 1, the two symmetrically indepen-
dent molecules are connected to each other through alternating
intermolecular strong N3eH1n3/O1 and N4eH1n4/O2 hydrogen
bonds to form a one dimensional polymeric chain. Besides, weak
intermolecular CeH/O hydrogen bonds generate a 3-D polymeric
chain in the crystal structure (Fig. 3). In complex 2, the N1e
H1n1/Cl1 strong intermolecular hydrogen bonds produce a 1-D
polymeric chain, which is completed in a 3-D network by weak
intermolecular CeH$O hydrogen bonds (Fig. 4).
3.3. Nanoparticle preparation
Nowadays, many chemists employ the ultrasonic method for
the synthesis of nanoscale organic/inorganic compounds [44e
46]. The apparent advantage of this technique lies in a straight-
forward methodology and possibility to use a relatively simple
apparatus [47,48]. The nanoparticles of compounds 1, 2 were
prepared by performing the synthesis in an ultrasonic bath at
30 ꢁC for about 1 h. It is notable that nanoparticles can be ob-
tained from both dissolved and powdered samples. For the dis-
solved samples, some droplets of them are placed on a small
piece of foil while the powdered compounds are directly placed
on the sample holder for taking the SEM images. Here, the
complexes were dissolved in methanol and after evaporation of
the solvent, the SEM images were obtained from the nano-
particles prepared on aluminum foil.
The SEM micrographs shown in Figs. 5 and 6 indicate the par-
ticle sizes are about 15e20 nm with an identical spherical
morphology. The XRD patterns in Fig. 7 indicate sharp peaks due to
high crystallinity with the sharpest peaks for compounds 1, 2
appear at 2q
values of 15.9ꢁ and 9.5ꢁ, respectively. Using Debyee
Scherrer equation [49], the crystal sizes of compounds 1, 2 were
estimated from the XRD diagrams about 38.10 and 69.23 nm,
respectively.
4. Conclusions
The synthesis, X-ray crystallography and nanoparticle prepara-
tion of a new phosphoric triamide (1) and an organotin(IV) complex
(2) were performed. Compound 1 revealed two symmetrically in-
dependent molecules in the crystal lattice and compound 2 showed
Fig. 7. The XRD patterns of the nanoform of the compounds 1 (a) and 2 (b).

438
Z. Shariatinia et al. / Journal of Organometallic Chemistry 745-746 (2013) 432e438
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