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Two novel diorganotin phosphonic diamides syntheses crystal structures spectral properties and in vitro antibacterial studies.

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Full Paper
Received: 30 January 2010
Revised: 6 April 2010
Accepted: 13 March 2010
Published online in Wiley Online Library: 28 June 2010
(wileyonlinelibrary.com) DOI 10.1002/aoc.1669
Two novel diorganotin phosphonic diamides:
syntheses, crystal structures, spectral
properties and in vitro antibacterial studies
Khodayar Gholivanda∗ , Sedigheh Farshadiana , Zahra Hosseinia ,
Khosro Khajehb and Neda Akbarib
Two diorganotin complexes with general formulae SnCl2 (CH3 )2 [C6 H5 P(O)(NHCH(CH3 )2 )2 ]2 (1) and SnCl2 (CH3 )2 [C6 H5 P(O)
(NHC(CH3 )3 )2 ] (2) were prepared by the addition of one equivalent SnCl2 Me2 to two equivalents of PhP(O)(NHi Pr)2 and
PhP(O)(NHt Bu)2 , respectively. The compounds were characterized by elemental analysis, IR and multinuclear NMR (1 H, 13 C,
31 P and 119 Sn) spectroscopy. The crystal structures of the complexes were determined by X-ray single crystal analysis, which
revealed that complex 1 has a distorted octahedral geometry and complex 2 has a distorted trigonal bipyramidal structure with
non-equivalent chlorine atoms. Preliminary antibacterial tests of the compounds against Gram-positive and -negative bacteria
c
were carried out using the filter paper disk method and chloroamphenicol was used as standard for comparison. Copyright 2010 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: phosphonic diamide; diorganotin; NMR; X-ray structures; antibacterial activity
Introduction
700
Organotin compounds are of great interest and they have
been the subject of diverse studies owing to their anticancer
activity[1] as well as their applications as biocides.[2] In recent
years several organotin derivatives with P-containing donors
have been reported in literature,[3] due to their convenience
for spectroscopic NMR studies (31 P). Furthermore, the phosphorus compounds have wide agricultural applications because
of their potent biocidal effect[4] and the presence of both
organotin(IV) moieties and phosphorus moieties in a single
molecular could produce a still more powerful and lasting effective complex. Some of these complexes also exhibit antitumor
activity.[3e,h]
Tin complexes of phosphonic amides also have importance
due to potential use of chiral phosphoramides to catalyze the
enantioselective allylation of allyltrichlorosilanes.[5] In comparison
with weak complexation of phosphoramides to chlorosilanes[5]
they can bind much better to tin through their phosphoryl oxygen,
so to have a clear understanding of the phosphoramide Lewis acid
complex structure, it is important to investigate the reaction
of phosphonic diamide and organotin compounds. However,
survey of the literature reveals only one paper,[6] dealing with
the synthesis of the diorganotin complex of phosphonic diamide,
[Ph2 SnCl2 (t BuP(O)(NHi Pr)2 )2 ]. The Sn(IV) atom in this complex
exhibited a hypervalent octahedral geometry.
From the above consideration, in connection with our current
work on the coordination chemistry of diorganotin complexes with
phosphoryl containing ligands,[7] and to investigate the influence
of substituents on the nitrogen atoms in organotin geometries,
we used phenyl N,N -bis(isopropyl)phosphonic diamide and
phenyl N,N -bis(tert-butyl) phosphonic diamide ligands to react
with dimethyltin dichloride. Here we report the syntheses,
Appl. Organometal. Chem. 2010, 24, 700–707
spectroscopic characterization (1 H, 13 C, 31 P, 119 Sn NMR and IR) and
crystal structures of these new diorganotin complexes. Because
of the different steric and electronic features of isopropyl and
tert-butyl substituents on the nitrogen atoms, hexa-and pentacoordinated tin(IV) complexes were obtained. The compounds
were also screened for their antibacterial activity.
Experimental
All the chemicals used are commercially available and were used
as received without further purification. 1 H, 13 C, 31 P and 119 Sn NMR
spectra were recorded on a Bruker Avance DRS 500 spectrometer
at 500.13, 125.77, 202.46 and 186.50 MHz respectively. 1 H and
13 C chemical shifts were determined relative to internal Me
4
Si. 31 P and 119 Sn chemical shifts were measured relative to
85% H3 PO4 and Sn(CH3 )4 as external standards respectively.
Infrared (IR) spectra (4000–400 cm−1 ) were recorded on KBr
disks using 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.
Abbreviations used in multiplicities are: s, singlet; d, doublet;
dd, doublet of doublets; t, triplet; dt, doublet of triplets; m,
multiplet.
∗
Correspondence to: Khodayar Gholivand, Department of Chemistry, Faculty
of Sciences, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran.
E-mail: gholi kh@modares.ac.ir
a Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, PO
Box 14115-175, Tehran, Iran
b Department of Biochemistry and Biophysics, Faculty of Sciences, Tarbiat
Modares University, Tehran, Iran
c 2010 John Wiley & Sons, Ltd.
Copyright Two novel diorganotin phosphonic diamides
Synthesis of Ligands
Synthesis of C6 H5 P(O)[NHCH(CH3 )2 ]2
To a solution of PhP(O)Cl2 (0.820 g, 4.2 mmol) in CH3 CN (20 ml), a
solution of iso-propylamine (0.994 g, 16.8 mmol) in CH3 CN (10 ml)
was added dropwise at 0 ◦ C. After 12 h stirring, the solvent was
removed, the product was washed with distilled water and dried
(yield 0.45 g, 45%).
M.p. 154 ◦ C. Anal. calcd for C12 H21 N2 OP: C, 59.98; H, 8.81; N,
11.66. Found: C, 59.94; H, 8.80; N, 11.68%. 1 H NMR (CDCl3 , ppm):
δ 1.09 (d, 6H, 3 JHH = 6.4 Hz, CH3 ), 1.12 (d, 6H, 3 JHH = 6.4 Hz,
CH3 ), 2.24 (m, 2H, NH), 3.43 (m, 2H, 3 JHH = 6.6 Hz, CH), 7.41
(dt, 3 JHH = 7.3 Hz, 4 JPH = 3.1 Hz, 2H, P–C6 H5 -meta), 7.47 (t,
3J
3
HH = 7.4 Hz, 1H, P–C6 H5 -para), 7.83 (dd, JPH = 12.2 Hz, 2H,
3
13
JHH = 8.0 Hz, P–C6 H5 -ortho). C NMR (CDCl3 , ppm): δ 24.28 (d,
3J
3
PC = 4.9 Hz, CH3 ), 24.35 (d, JPC = 6.4 Hz, CH3 ), 41.43 (s, CH),
126.65 (d, 3 JPC = 13.1 Hz, P–C6 H5 -meta), 129.61 (d, 4 JPC = 2.3 Hz,
P–C6 H5 -para), 130.05 (d, 2 JPC = 9.3 Hz, P–C6 H5 -ortho), 132.70 (d,
1J
31
PC = 150.9 Hz, P–C6 H5 -ipso). P NMR (CDCl3 , ppm): δ 17.82 (m).
IR (KBr, cm−1 ): ν = 3200 (s, NH), 2940 (m), 1459 (m), 1427 (m), 1379
(w), 1180 (s, P O), 1158 (s), 1137 (s), 1110 (m), 1039 (s), 1006 (m),
902 (m, P–N), 870 (w), 839 (w), 740 (m), 689 (m), 551 (m), 517 (m).
Synthesis of C6 H5 P(O)[NHC(CH3 )3 ]2
This ligand was prepared by a modified procedure given in the
literature.[8] To a 20 ml CH3 CN solution of PhP(O)Cl2 (0.688 g,
3.53 mmol) was added a solution of tert-butylamine (1.03 g,
14.12 mmol) in CH3 CN (10 ml) dropwise with continuous stirring
in an ice bath. After 12 h stirring at room temperature the solvent
was removed, and the product was washed with distilled water
and dried (yield 0.605 g, 64%).
M.p. 182 ◦ C. Anal. calcd for C14 H25 N2 OP: C, 62.66; H, 9.39; N, 10.44.
Found: C, 62.62; H, 9.41; N, 10.5%. 1 H NMR (CDCl3 , ppm): δ 1.28 (s,
18H, CH3 ), 2.38 (d, 2H, 2 JPH = 9.1 Hz, NH), 7.40 (m, 3H, P–C6 H5 -para,
meta), 7.82 (m, 3 JPH = 12.7 Hz, 3 JHH = 7.6 Hz, 2H, P–C6 H5 -ortho).
13
C NMR (CDCl3 , ppm): δ 32.02 (d, 3 JPC = 4.2 Hz, CH3 ), 51.78
[s, C (CH3 )3 ], 128.01(d, 3 JPC = 13.3 Hz, P–C6 H5 -meta), 130.71 (d,
4
JPC = 2.4 Hz, P–C6 H5 -para), 131.43 (d, 2 JPC = 9.5 Hz, P–C6 H5 ortho), 137.74 (d, 1 JPC = 156.3 Hz, P–C6 H5 -ipso). 31 P NMR (CDCl3 ,
ppm): δ 14.77 (broad). 1 H NMR (DMSO-d6 , ppm): δ 1.14 (s, 18H,
CH3 ), 3.79 (d, 2H, 2 JPH = 9.1 Hz, NH), 7.39 (m, 3 JHH = 6.7 Hz, 3H,
P–C6 H5 -para, meta), 7.74 (dd, 3 JPH = 12.2 Hz, 3 JHH = 7.7 Hz, 2H,
P–C6 H5 -ortho). 13 C NMR (DMSO-d6 , ppm): δ 31.61 (d, 3 JPC = 4.1 Hz,
CH3 ), 50.62 [s, C(CH3 )3 ], 127.50 (d, 3 JPC = 12.7 Hz, P–C6 H5 -meta),
129.85 (d, 4 JPC = 2.6 Hz, P–C6 H5 -para), 131.34 (d, 2 JPC = 9.5 Hz,
P–C6 H5 -ortho), 139.43 (d, 1 JPC = 148.6 Hz, P–C6 H5 -ipso). 31 P NMR
(DMSO-d6 , ppm): δ 13.61 (m, 2 JPH = 9.8 Hz). IR (KBr, cm−1 ):
ν = 3390 (w, NH), 3210 (m, NH), 3205 (w), 2980 (m), 1462 (w),
1424 (m), 1380 (m), 1219 (s, P O), 1182 (s), 1115 (m), 1006 (s), 857
(w), 749 (w), 724 (w), 570 (m), 539 (w).
Synthesis of complexes 1 and 2
SnCl2 (CH3 )2 {C6 H5 P(O)[NHCH(CH3 )2 ]2 }2 (1)
Appl. Organometal. Chem. 2010, 24, 700–707
SnCl2 (CH3 )2 {C6 H5 P(O)[NHC(CH3 )3 ]2 } (2)
To a stirred solution of C6 H5 P(O)[NHC(CH3 )3 ]2 (132 mg, 0.5 mmol),
a solution of (CH3 )2 SnCl2 (54 mg, 0.25 mmol) in 10 ml of toluene
was added and heated (50–60 ◦ C) for 2 h. The resulting mixture
was then stirred at room temperature overnight. The mixture was
filtered and the solvent was evaporated to give a white powder.
Recrystallization of the powder in dichloromethane–hexane (1 : 1,
v/v) mixture produced single crystals of 2.
M.p. 167 ◦ C. Anal. calcd for C16 H31 Cl2 N2 OPSn: C; 39.38; H, 6.40;
N, 5.74%. Found: C; 39.39; H, 6.40; N, 5.72%. 1 H NMR (CDCl3 , ppm):
δ 1.21 [6H, 2 J(119/117 Sn, 1 H) = 81.7 Hz, Sn(CH3 )2 ], 1.30 (s, 18H, CH3 ),
2.55 (d, 2H, 2 JPH = 10.1 Hz, NH), 7.45 (td, 3 JHH = 7.7 Hz, 4 JPH = 4.3,
2H, P–C6 H5 -meta), 7.49 (dt, 3 JHH = 7.7 Hz, 1H, P–C6 H5 -para), 7.85
(dd, 3 JPH = 13.5 Hz, 3 JHH = 6.75 Hz, 2H, P–C6 H5 -ortho). 13 C NMR
(CDCl3 , ppm): δ 13.30 (s, SnCH3 ), 1 J(119 Sn, 13 C) = 665.1 Hz) 32.01
(d, 3 JPC = 4.3 Hz, CH3 ), 52.23 [s, C(CH3 )3 ], 128.42 (d, 3 JPC = 13.7,
P–C6 H5 -meta), 131.50 (d, 2 JPC = 10.6 Hz, P–C6 H5 -ortho), 131.63 (d,
4J
1
PC = 2.4 Hz, P–C6 H5 -para), 135.44 (d, JPC = 157.7 Hz, P–C6 H5 31
ipso). P NMR (CDCl3 , ppm): δ 15.04 (s). 1 H NMR (DMSO-d6 , ppm):
δ 1.03 [6H, 2 J(119/117 Sn, 1 H) = 112.9 Hz, Sn(CH3 )2 ], 1.14 (s, 18H,
CH3 ), 3.77 (d, 2H, 2 JPH = 8.8 Hz, NH), 7.39 (m, 3H, P–C6 H5 -para,
meta), 7.75 (m, 2H, P–C6 H5 -ortho). 13 C NMR (DMSO-d6 , ppm):
δ 23.15 [s, Sn–CH3 , 1 J(119 Sn, 13 C) = 1005.7 Hz, 1 J(117 Sn, 13 C)
= 956.3 Hz], 31.58 (d, 3 JPC = 4.2 Hz, CH3 ), 50.60 [s, C(CH3 )3 ],
127.46 (d, 3 JPC = 12.8 Hz, P–C6 H5 -meta), 129.83 (d, 4 JPC = 2.3 Hz,
P–C6 H5 -para), 131.31 (d, 2 JPC = 9.5 Hz, P–C6 H5 -ortho), 139.4 (d,
1J
31
PC = 148.5 Hz, P–C6 H5 -ipso). P NMR (DMSO-d6 , ppm): δ 13.60
2
119
(m, JPH = 9.4 Hz). Sn NMR (DMSO-d6 , ppm): −238.2 119 Sn NMR
(CD3 OD, ppm): δ −106.62. IR (KBr, cm−1 ): ν = 3410 (m, NH), 3235
(m, NH), 2905 (s), 1469 (w), 1431 (m), 1361 (m), 1225 (s), 1187 (s),
1146 (s, P O), 1115 (s), 1040 (m), 1009 (s), 860 (w), 787 (w), 729
(w), 707 (w), 570 (m), 565 (w, Sn–C), 436 (w, Sn–O).
Crystal Structure Determination
X-ray data of compounds 1 and 2 were collected on a Bruker
SMART 1000 CCD area detector[9] with graphite-monochromated
Mo Kα radiation (k = 0.71073 Å). The structures were refined with
SHELXL-97[10] by full-matrix least squares on F2 . The positions
of hydrogen atoms were obtained from the difference Fourier
map. Crystal data and experimental details of the structure
determinations are listed in Table 2.
In Vitro Antibacterial Activity
The in vitro antibacterial activities of the ligands and their
organotin (IV) derivatives were tested by using the filter paper disk method.[11] The bacteria were cultured in nutrient agar
c 2010 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
701
Dimethyltin dichloride (70 mg, 0.32 mmol) was added to an
acetonitrile solution (10 ml) of C6 H5 P(O)[NHCH(CH3)2 ]2 (152 mg,
0.64 mmol) and stirred at room temperature. After 10 days, the
solvent was allowed to evaporate slowly and the suitable single
crystals of 1 were obtained after 5 days (yield 80 mg, 71%).
M.p. 134 ◦ C. Anal. calcd for C26 H48 Cl2 N4 O2 P2 Sn: C, 44.60; H, 6.91;
N, 8.00. Found: C, 44.56; H, 6.90; N, 7.98%. 1 H NMR (CDCl3 , ppm):
δ 1.12 (dd, 24H, 3 JHH = 6.7 Hz, CH3 ), 1.25 [6H, 2 J(119/117 Sn, 1 H) =
88.9 Hz, Sn(CH3 )2 ], 2.60 (dd, 4H, 2 JPH = 9.0 Hz, NH), 3.39 (m, 4H,
3
JHH = 6.4 Hz, CH), 7.45 (dt, 3 JHH = 7.4 Hz, 4 JPH = 3.6, 4H, P–C6 H5 meta), 7.51 (dt, 3 JHH = 7.3 Hz, 4 JPH = 1.3 Hz, 2H, P–C6 H5 -para),
7.78 (dd, 3 JPH = 14.0 Hz, 3 JHH = 8.3, 4H, P–C6 H5 -ortho). 13 C NMR
(CDCl3 , ppm): δ 20.93 [s, Sn–CH3 , 1 J(119 Sn, 13 C) = 1214.1 Hz], 25.70
(d, 3 JPC = 2.3 Hz, CH3 ), 25.74 (d, 3 JPC = 2.0 Hz, CH3 ), 43.29 (s, CH),
128.49 (d, 3 JPC = 13.5 Hz, P–C6 H5 -meta), 131.55 (d, 2 JPC = 9.8 Hz,
P–C6 H5 -ortho), 131.79 (d, 4 JPC = 2.8 Hz, P–C6 H5 -para), 132.60 (d,
1J
31
PC = 155.1 Hz, P–C6 H5 -ipso). P NMR (CDCl3 , ppm): δ 18.37 (m).
119 Sn NMR (CD OD, ppm): δ −118.56. IR (KBr, cm−1 ): ν = 3240 (m,
3
N–H), 2945 (m), 1453 (w), 1417 (m), 1382 (w), 1138 (s, P O), 1103
(s), 1019 (w), 902 (w), 702 (w), 744 (w), 576 (w, Sn–C), 551 (m), 491
(w, Sn–O).
K. Gholivand et al.
medium and used as inocula. The solvent used in control was
dichloromethane. Whatmann filter paper disks (diameter 6.5 mm)
were saturated with the solutions of the test compound (concentration 5 and 10 mg ml−1 ) or reference drug, chloroamphenicol
(concentration 5 and 10 mg ml−1 ). These disks were then placed
on the surface of a sterilized agar nutrient medium that was inoculated with test bacteria and air-dried to remove the surface
moisture. The thickness of the agar medium was kept equal in
all Petri dishes. A control disk (saturated with solvent) without
the test compound was similarly treated. Thereafter, the disks
were incubated at 37 ± 1 ◦ C for 20–24 h. The zone of inhibition
of growth was measured, which indicates the inhibitory activity
of the compounds on the growth of the bacteria. The average of
three diameters was calculated for each sample.
Results and Discussion
Synthesis and Spectral Characterization
The six-coordinate organotin 1 was obtained from the reaction
of Me2 SnCl2 with 2 equivalents PhP(O)(NHi Pr)2 in acetonitrile
solution at room temperature, but PhP(O)(NHt Bu)2 does not react
with SnCl2 Me2 under the conditions used for the synthesis of 1.
Treatment of a toluene solution of this ligand with Me2 SnCl2 in
a 2 : 1 ratio in 50 ◦ C, afforded 1 : 1 (ligand : tin) adduct and fivecoordinated hypervalent organotin was obtained (Scheme 1). A
similar reaction using PhP(O)(NHi Pr)2 ligand was also conducted
and resulted in the formation of complex 1 again. In this case
the five-coordinated organotin was not observed. Therefore the
2 : 1 and 1 : 1 complexes are independent of type of solvent and
molar ratio of ligand to tin (2 : 1 or 1 : 1) and they depend on
the different steric and electronic features of the ligands. Some
spectroscopic data of compounds 1 and 2 and their corresponding
ligands are listed in Table 1. Solvent effects on chemical shifts
were investigated using CDCl3 and DMSO-d6 for complex 2 and
PhP(O)(NHt Bu)2 .
The 1 H NMR spectrum of the complex 1 in CDCl3 solution is
consistent with the formula of 2 : 1 adduct, which exhibits the
expected proton signals for two equivalent ligands and the tinproton coupling constant 2 J(119 Sn, 1 H), falling in the range for
six-coordinated dimethyltin (IV) species.[12] Signals due to these
methyl protons in CDCl3 appear at 1.25 and 1.21 ppm for 1 and
2, respectively. In DMSO-d6 solution of 2 this signal appears at
1.03 ppm and the value of 2 J(119 Sn– 1 H) coupling constant, about
112.9 Hz, reveals a six-coordinated tin atom in a coordinating
solvent for 2 and the complex does not retain solid-state structure
in this solution.
Scheme 1. The preparation pathway for the synthesis of compounds.
702
wileyonlinelibrary.com/journal/aoc
The methyl protons of the two isopropyl groups of
PhP(O)(NHi Pr)2 appear as two different doublets at 1.09 and
1.11 ppm (3 JHH = 6.4 Hz). For 1 a triplet (two overlapping doublets) is observed for these protons at 1.12 ppm (3 JHH = 6.7 Hz).
Only one signal for 18 methyl protons of the tert-butyl groups
for 2 and PhP(O)(NHt Bu)2 is observed. The 1 H NMR spectrum
of PhP(O)(NHi Pr)2 shows a broad peak for the amino protons at
2.24 ppm and the spectrum of 1 shows a triplet (which is actually
two overlapping doublets) at 2.60 ppm (2 JPH = 9.1 Hz) due to the
presence of two different types of N–H protons in the molecules.
The same result was also observed in the previous reported organotin complex of phosphonic diamide.[6] For PhP(O)(NHt Bu)2 a
doublet peak (2 JPH = 9.1 Hz) is observed for the amino protons at
2.38 ppm in CDCl3 and 3.79 ppm in DMSO-d6 . The amino protons
of compound 2 appear at 2.55 ppm (2 JPH = 10.1 Hz) in CDCl3
and at 3.77 ppm (2 JPH = 8.8 Hz) in DMSO-d6 . Because of the poor
hydrogen bonding of CDCl3 compared to DMSO-d6 [13] , the NH
resonance tends to be more shielded and subsequently appears
more upfield.
In the 13 C NMR spectra, two CH3 carbons of the two isopropyl
groups are not equivalent and we observe two 3 J(P,C) coupling
constants 4.9 and 6.4 Hz for PhP(O)(NHi Pr)2 that decreased to 2.3
and 2.0 Hz in complex 1. Signals for the aryl carbons except for
the ipso carbons are slightly shifted to low field compared with
the free ligands in CDCl3 solution; the shift is a consequence of an
electron density transfer from the ligands to the metal atom. Also,
the coupling between phosphorus and all of the aromatic carbon
atoms is observed as these values (n JPC , n = 1, 2, 3, 4) are larger
for the complexed ligand than for the free ones (Table 1).
The value of the coupling constant 1 J(119/117 Sn– 13 C) for 1,
1214.1 Hz, is indicative of a six-coordinated compound. In the
concentrated DMSO-d6 solution of 2, both of the 1 J(119 Sn– 13 C)
and 1 J(117 Sn– 13 C) coupling constants are observed; the values
of 1005.7 and 956 Hz respectively reveal a six-coordinated tin
atom.[12]
The 31 P NMR chemical shifts are observed at about 18.37
and 15.04 ppm in CDCl3 solution for 1 and 2 respectively.
The downfield chemical shift in comparison to that of free
ligands (Table 1) indicates a considerable drift of electron density
from the phosphorus to the tin atom through the oxygen
atom.[14] Noticeable chemical shift differences are observed for
PhP(O)(NHt Bu)2 (Table 1) in varying the solvent. This difference
is also related to the poor hydrogen bonding of CDCl3 with
electronegative atoms compared with DMSO-d6 .
The single resonance at −238.2 ppm in the 119 Sn NMR spectrum
of compound 2 in DMSO-d6 solution provides additional support
for six-coordinated tin atoms in this solution.[15] Because of the
poor solubility of complexes in CDCl3 , CD3 OD was used as a solvent
in the 119 Sn NMR spectroscopic measurements. The 119 Sn NMR
spectrum of complex 1 shows only one signal at −118.56 ppm.
This chemical shift is not informative enough, as it can belong
to penta- or weakly hexacoordinate species in solution.[16] The
chemical shift for 2 is observed at −106.62 ppm, which is typical
of a five-coordinated species[15] and is in accordance with the
solid-state structure.
In the solid-state IR spectra, the N–H stretching vibration in
ligands result in an absorption in 3200 cm−1 for PhP(O)(NHi Pr)2
and two absorptions in 3210 and 3205 cm−1 for PhP(O)(NHt Bu)2 .
In the organotin (IV) complexes this band shifts to higher energy,
suggesting an important influence of the coordination to tin, and
is consistent with the presence of a hydrogen bond between the
N–H moiety and the halide groups. The negative significant shift
c 2010 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2010, 24, 700–707
Two novel diorganotin phosphonic diamides
Table 1. Spectroscopic NMR and IR data of the compounds
Compound
δ 31 P
(ppm)
PhP(O)(NHi Pr)2
17.82
br
–
PhP(O)(NHt Bu)2
14.77
13.61
18.37
9.1
9.1
9.0
–
–
88.9
15.04
13.60
10.1
8.8
81.7
112.9
1
2
2
JPNH
(Hz)
2 119
J(
SnH)
(Hz)
3
J(P,Caliphatic )
(Hz)
4.9
6.4
4.2
4.1
2.3
2.0
4.3
4.2
Figure 1. Molecular structure and atom labeling scheme for 1 (40%
probability ellipsoids).
of the ν(P O) in the spectra of complexes with respect to the free
ligands (42 cm−1 for 1 and 73 cm−1 for 2) is in accordance with
the coordination of the phosphoryl oxygen atom to tin.
An absorption appears at 491 and 465 cm−1 in the respective
spectra of complexes 1 and 2 respectively, which are absent in the
spectra of the free ligands. This is assigned to the Sn–O stretching
mode of vibration.
X-ray Crystallography Investigation
SnCl2 (CH3 )2 {C6 H5 P(O)[NHCH(CH3 )2 ]2 }2 (1)
Appl. Organometal. Chem. 2010, 24, 700–707
J(P,C)
(Hz)
2
J(P,C)
(Hz)
3
J(P,Caromatic )
(Hz)
4
J(P,C)
Hz
Solvent
ν(P O)
(cm−1 )
150.9
9.3
13.1
2.3
CDCl3
1180
155.1
148.6
156.3
9.5
9.5
9.8
13.3
12.7
13.5
2.4
2.6
2.8
CDCl3
DMSO-d6
CDCl3
1219
157.7
148.5
10.6
9.5
13.7
12.8
2.4
2.3
CDCl3
DMSO-d6
1146
1138
Figure 2. Formation of one-dimensional polymeric chain in 1 through
N–H· · ·Cl hydrogen bonds.
reverse). These Sn–O bond lengths are a little longer than the
Sn–O covalent bond lengths (2.038–2.115 Å).[18]
The data for hydrogen bonding are presented in Table 5. One
of the two N–H linkages on each phosphonic diamide is involved
in hydrogen bonding with chlorine atom of the same molecule, so
two six-membered rings around tin are formed. These rings, which
made up six different elements coming from five different groups
of the main group [group 1 (H), group 14 (Sn), group 15 (N, P), group
16 (O), group 17 (Cl)] were also observed in our previously reported
organotin compounds[7] and in {Ph2 SnCl2 [t BuP(O)(NHi Pr)2 ]2 }.[6]
The other N–H group on each phosphonic diamide is involved
in intermolecular hydrogen bonding with the chlorine of a
neighboring molecule and one-dimensional polymeric structures
(shown in Fig. 2 along the a-axis) were obtained. Furthermore,
the presence of cooperative intermolecular π interactions between carbon atoms [C11· · ·C25 (3.377 Å), C12· · ·C22 (3.394 Å),
C13· · ·C23 (3.368 Å), C8· · ·C22 (3.392 Å)], carbons and protons
[C–H26· · ·C19 (2.817 Å), C–H14· · ·C5 (2.684 Å)], oxygens and protons [O1· · ·H16–C (2.677 Å), O2· · ·H8–C (2.677 Å)], C–H11· · ·Cl1
(2.949 Å) and C–H7· · ·H15–C (2.370 Å) in the crystal also stabilize
the structure and produce a three-dimensional network in the
crystalline lattice.
SnCl2 (CH3 )2 {C6 H5 P(O)[NHC(CH3 )3 ]2 } (2)
Single crystals of 2 suitable for single crystal X-ray diffraction
analysis were obtained from CH2 Cl2 /n-hexane by slow evaporation
of the solvent. The compound crystallizes in the space group
P21 /n with four discrete molecules in the unit cell. The molecular
structure of complex 2 is illustrated in Fig. 3, and selected bond
lengths and bond angles are given in Table 4.
In 2 the geometry at tin becomes distorted trigonal bipyramidal
with the oxygen of the phosphonic diamide and chlorine
c 2010 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
703
Colorless crystals of 1 suitable for X-ray diffraction analysis were
grown from a concentrated CH3 CN solution at room temperature.
The compound crystallizes in the space group Pna21 with four
discrete molecules in the unit cell. Figure 1 shows an ORTEP
representation of the molecular structure for this complex, and
the selected bond distances and angles are listed in Table 3.
The complex contains a hexa-coordinated tin atom and has a
slightly distorted octahedral environment. Identical ligands (the
two methyl groups, the two phosphonic diamides and the two
chlorine atoms) are in trans positions and the trans bond angles
around Sn atom are in the range 177.50–178.52◦ . The different
ligands are cis to each other and C–Sn–O, C–Sn–Cl and O–Sn–Cl
bond angles are in the range of 87.54–92.97◦ (Table 3). The Sn–C
bond lengths are 2.114(4) and 2.117(4) Å, which are consistent
with those reported in other organotin(IV) complexes. The Sn–Cl
bond lengths [2.6075(8) and 2.6150(8) Å] are slightly greater than
normal covalent radii, 2.37–2.60 Å,[17] and those found for other
diorganotin compounds. Two different Sn–O distances [2.194(2)
and 2.220(2) Å] and also two different P–O–Sn angles [144.06(13)
and 149.04(13)◦ ] can be observed in complex 1. The shorter Sn–O
distances correspond to the larger P–O–Sn angles (and the
1
K. Gholivand et al.
Table 2. Crystal data collection and structure refinement parameters for complexes 1 and 2
Compound
Formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
β (deg)
V (Å 3 )
Z
Dcalc (mg m−3 )
Absorption coefficient (mm−1 )
F(000)
Crystal size (mm3 )
Theta range for data collection (deg)
Index ranges
Reflections collected/unique (Rint )
Completeness to θ (%)
Absorption correction
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F 2
Final R indices
R indices (all data)
Largest difference in peak and hole (eÅ 3 )
1
2
C26 H48 Cl2 N4 O2 P2 Sn
700.21
100(2)
0.71073
Orthorhombic
P na21
8.5988(5)
24.7398(12)
16.1831(8)
90
3442.7(3)
4
1.351
1.018
1448
0.17 × 0.11 × 0.10
1.50–28.00
−11 ≤ h ≤ 11
−32 ≤ k ≤ 26
−21 ≤ l ≤ 19
23168/7872 (0.0441)
100.0
Semi-empirical from equivalents
0.909 and 0.840
Full-matrix least-squares on F 2
7872/1/334
0.997
R1 = 0.0317
wR2 = 0.0551
R1 = 0.0412
wR2 = 0.0581
0.812 and −0.623
C16 H31 Cl2 N2 OPSn
487.99
100(2)
0.71073
Monoclinic
P21/n
9.5525(5)
13.8242(7)
17.1520(9)
98.8260(10)
2238.2(2)
4
1.448
1.457
992
0.25 × 0.17 × 0.12
1.90–29.00
13 ≤ h ≤ 13
−18 ≤ k ≤ 18
−23 ≤ l ≤ 23
26831/5931 (0.0287)
99.8
Semi-empirical from equivalents
0.8446 and 0.7122
Full-matrix least-squares on F 2
5931/0/180
1.019
0.0411
wR2 = 0.0863
R1 = 0.0522
wR2 = 0.0923
2.187 and −1.138
Figure 3. Molecular structure and atom labeling scheme for compound 2
(50% probability ellipsoids).
704
atoms in axial sites [Cl(2)–Sn(1)–O(1), 173.71(7)] and another
chlorine and two carbon atoms occupying the equatorial plane
[C(1)–Sn(1)–C(2) = 130.9(2), C(1)–Sn(1)–Cl(1) = 119.62(15);
C(2)–Sn(1)–Cl(1) = 108.84(15)]. The sum of the angles subtended
at the tin atom in the trigonal plane is 359.36, so that the atoms
Sn(1), C(1), C(2) and C(1) are almost in the same plane and
the deviations from the equatorial plane are −0.096 Å for Sn(1),
−2.595 Å for Cl(2) and 2.159 Å for O(1).
wileyonlinelibrary.com/journal/aoc
According to Reedijk’s criteria,[19] the geometry around Sn
atom can be characterized by the value of τ = (β − α)/60,
where τ = 0 for a perfect square pyramidal and τ = 1 for
perfect trigonal–bipyramidal. The calculated τ value for complex
2 (β = 173.71◦ and α = 119◦ ) is 0.90, indicating a highly distorted
trigonal bipyramidal arrangement around the Sn atom.
The two Sn–Cl bond lengths lie in the range of the normal
covalent radii,[17] but are not equivalent, the trans to O atom
being longer than the other [Sn(1)–Cl(1), 2.3510(11) Å, equatorial
bond, and Sn(1)–Cl(2), 2.5037(10) Å, axial bond]. This finding is
consistent with the observation that the difference between axial
and equatorial lengths increases markedly upon replacement of
one or more of five identical ligands with more electropositive
groups in a trigonal bipyramidal coordination.[20]
The Sn–O bond distance [Sn(1)–O(1), 2.258(2) Å] is longer than
the sum of the covalent bond radii of Sn and O,[18] but considerably
shorter than the sum of their van der Waals radii of 3.71 Å.[21]
The P O bond length in this molecule is 1.493(2) Å, which is
larger than the normal P O bond length (1.45 Å).[22] The P O
bond length in this complex is equal to our previous reported
organotin complex of a phosphoramidate with tert-butyl groups in
its structure, and it is longer than that of the corresponding ligand,
PhP(O)(NHt Bu)2 (1.477(2) Å).[8] This lengthening is consistent with
the low stretching frequency observed in the IR spectra and may
c 2010 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2010, 24, 700–707
Two novel diorganotin phosphonic diamides
Table 3. Selected bond lengths and bond angels for complex 1
Bond
Distance (Å)
Sn(1)–C(1)
Sn(1)–C(2)
Sn(1)–O(2)
Sn(1)–O(1)
Sn(1)–Cl(1)
Sn(1)–Cl(2)
2.114(4)
2.117(4)
2.194(2)
2.220(2)
2.6075(8)
2.6150(8)
P(1)–O(1)
P(1)–N(2)
P(1)–N(1)
P(2)–O(2)
P(2)–N(3)
P(2)–N(4)
1.505(2)
1.628(3)
1.637(3)
1.502(2)
1.621(3)
1.637(3)
Angle
Amplitude
(deg)
178.52(15)
92.54(11)
91.28(12)
87.54(11)
177.50(8)
90.33(11)
89.53(6)
92.97(6)
88.25(6)
Angle
Amplitude
(deg)
89.25(6)
177.78(3)
119.09(13)
107.46(13)
104.10(14)
118.62(13)
104.82(13)
108.57(13)
103.65(14)
C(1)–Sn(1)–C(2)
C(2)–Sn(1)–O(2)
C(1)–Sn(1)–O(1)
C(2)–Sn(1)–O(1)
O(2)–Sn(1)–O(1)
C(1)–Sn(1)–Cl(1)
O(2)–Sn(1)–Cl(1)
O(1)–Sn(1)–Cl(1)
O(2)–Sn(1)–Cl(2)
Bond
O(1)–Sn(1)–Cl(2)
Cl(1)–Sn(1)–Cl(2)
O(1)–P(1)–N(2)
O(1)–P(1)–N(1)
N(2)–P(1)–N(1)
O(2)–P(2)–N(3)
N(3)–P(2)–N(4)
O(2)–P(2)–C(21)
N(3)–P(2)–C(21)
Distance (Å)
Table 4. Selected bond lengths and bond angels for complex 2
Bond
Distance (Å)
Sn(1)–C(1)
Sn(1)–C(2)
Sn(1)–O(1)
Sn(1)–Cl(1)
2.108(4)
2.109(4)
2.258(2)
2.3510(11)
Sn(1)–Cl(2)
P(1)–O(1)
P(1)–N(1)
P(1)–N(2)
2.5037(10)
1.493(2)
1.626(3)
1.632(3)
Angle
Amplitude
(deg)
130.9(2)
87.93(14)
89.26(13)
119.62(15)
108.84(15)
84.86(7)
95.95(12)
173.71(7)
Angle
Amplitude
(deg)
90.11(4)
116.17(16)
108.15(15)
107.38(16)
110.55(15)
102.05(16)
112.53(16)
151.37(16)
C(1)–Sn(1)–C(2)
C(1)–Sn(1)–O(1)
C(2)–Sn(1)–O(1)
C(1)–Sn(1)–Cl(1)
C(2)–Sn(1)–Cl(1)
O(1)–Sn(1)–Cl(1)
C(2)–Sn(1)–Cl(2)
O(1)–Sn(1)–Cl(2)
Bond
Cl(1)–Sn(1)–Cl(2)
O(1)–P(1)–N(1)
O(1)–P(1)–N(2)
N(1)–P(1)–N(2)
O(1)–P(1)–C(3)
N(1)–P(1)–C(3)
N(2)–P(1)–C(3)
P(1)–O(1)–Sn(1)
Distance (Å)
Appl. Organometal. Chem. 2010, 24, 700–707
Antibacterial Activity
The in vitro antibacterial activity of ligands and complexes was
performed against seven bacterial: three Gram-positive (Bacillus
subtilis, Bacillus cereus and Staphylococcus aureus) and four Gramnegative (Escherichia coli, Pseudomonas stutzeri, Pseudomonas
aeruginosa and Klebsiella pneumonia) and the results are summarized in Table 6. The antibacterial studies demonstrated that two
complexes have more activity toward tested bacteria than their
ligands, which show no activity at the same concentrations (5 and
10 mg ml−1 ). The ligands are active against Gram-positive bacteria
and some of the Gram-negative bacteria only at higher concentrations (40 mg ml−1 ). However, the complexation improves the
antibacterial properties and the antibacterial effect is, as expected,
proportional to the concentration of the compounds. As the
concentration is increased, tin complexes inhibit the growth of
bacteria to a greater extent. Complexes are more active against
the two bacteria, Staphylococcus aureus and Pseudomonas stutzeri,
than the parent organotin, (CH3 )2 SnCl2 . The most sensitive bacterial species on compounds tested are Gram-positive bacteria,
especially Staphylococcus aureus, while Gram-negative bacteria
Klebsiella pneumonia are the most resistant species.
These tin compounds exhibit a greater effect towards P. stutzeri,
P. aeruginosa and B. cereus compared with the reference drug
chloroamphenicol, which shows non-significant activity. Also,
these compounds show a comparable antibacterial effect to
chloroamphenicol against B. subtillus and S. aureus.
Supplementary Information
Crystallographic data for the structures 1 and 2 have
been deposited with Cambridge Crystallographic Data Center as supplementary publication numbers CCDC 709118
(C26 H48 Cl2 N4 O2 P2 Sn1 ) and CCDC 741999 (C16 H31 Cl2 N2 O1 P1 Sn1 ).
Copies of the data may be obtained, free of charge, on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (fax: +44 1223 336033; email: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk). Supporting information can also be
found in the online version of this article.
Acknowledgment
We wish to thank the Research Council of Tarbiat Modares
University for the financial support of this work.
c 2010 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
705
also explain the differences observed in the 31 P NMR chemical
shifts between the free and bound ligands in solution. On forming
complex 2 the ligand also shows a shortening of both the P–C
and P–N bond distances by about 0.013 Å for P–C and 0.02 and
0.012 Å for P–N bonds. This is accompanied by an increase in the
bond angles at the phosphorus atom, i.e. the C–P–N and N–P–N
angles are increased by 1.85, 1.23 and 2.78◦ respectively compared
with those of the free ligand.
The changes in bond distances are supported, in solution,
by an observed increase in the 1 JP – C coupling constant value
found in the complex compared with that in the free ligand.
Comparable changes in geometry, i.e. shortened bonds and
increased angles at the phosphorus atom, have been observed in
related complexes.[23]
In spite of the appreciable pyramidalization of the nitrogen
atoms in PhP(O)(NHt Bu)2 [the sum of the angles around N(1)
and N(2) are 358.8 and 350.7◦ respectively], in complex 2 the
nitrogen atoms are perfectly sp2 hybridized [the sum of angles
around each nitrogen atoms is 359.9 and 360◦ for N(1) and N(2)
respectively], and is capable of more effective hyperconjugation
with phosphorus.[24] The sum of angles around nitrogen atoms in
complex 1 are 353◦ and compared with the planar nitrogens in 2,
these nitrogens are pyramidal.
The intramolecular hydrogen bonds that formed six-membered
rings around tin atom in complex 1 are not seen in complex 2. Only
one intermolecular N–H· · ·Cl hydrogen bond exists in complex
2 (Table 5), which leads to 1D infinite chains in the crystal lattice
and one of the N–H bonds of each molecule not participating in
hydrogen bonding. Furthermore, the weak CH· · ·Cl intermolecular
interactions [C–H4· · ·Cl2 (2.935 Å) and C–H12· · ·Cl1 (2.928 Å)] also
stabilize the structure.
K. Gholivand et al.
Table 5. Hydrogen bonds for compounds 1 and 2
D–H–A
d(D–H) (Å)
d(H· · ·A) (Å)
N(1)–H(1)· · ·Cl(2) [x,y,z]
N(2)–H(2)· · ·Cl(2) [x + 1, y, z]
N(3)–H(3)· · ·Cl(1) [x − 1, y, z]
N(4)–H(4)· · ·Cl(1) [x,y,z]
N(1)–H(1)· · ·Cl(2) [x,y,z]
0.96
0.82
0.91
0.92
0.96
2.40
2.66
2.52
2.52
2.84
Complex
1
2
d(D· · ·A) (Å)
<DHA (deg)
3.310(3)
3.398(3)
3.370(3)
3.383(3)
3.634
158
149
154
157
153
Table 6. Inhibition zone (mean diameter of inhibition in mm) as a criterion of antibacterial activities of the synthesized compounds
Sample
1
2
PhP(O)(NHi Pr)2
PhP(O)(NHt Bu)2
Me2 SnCl2
Chloramphenicol
Concentration
(mg ml−1 )
P. aeruginosa
P. stutzori
E. coli
K. pneumonia
B. cereus
B. subtillus
S. aureus
5
10
5
10
5
10
40
5
10
40
5
10
5
10
13
18
7
15
–
–
–
–
–
–
17
21
–
7
15
20
15
19
–
–
12
–
–
7
12
18
–
–
10
13
6
13
–
–
15
–
–
13
8
13
13
17
7
10
10
12
–
–
12
–
–
–
14
20
11
15
18
22
20
23
–
–
10
–
–
10
18
25
12
15
15
17
15
18
–
–
12
–
–
6
17
20
14
17
20
25
18
22
–
–
7
–
–
6
16
22
17
22
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