Two conformers in the solid state for a novel organotin(IV) complex of a phosphoramidate: Syntheses, spectroscopic study and crystal structures of several new organotin(IV) complexes of N-benzoylphosphoric triamides

Article abstract of DOI:10.1016/j.jorganchem.2006.06.032

Several novel organotin(IV) complexes with formula SnCl₂(CH₃)₂(X)₂, X = C₆H₅C(O)NHP(O)(NC₄H₈) ₂ (1), C₆H₅C(O)NHP(O)(NC₅H₁₀) ₂ (2), C₆H₅C(O)NHP(O)[N(CH₃)(C₆ H₁₁)]₂ (3), C₆H₅C(O)NHP(O)[NH-C(CH₃)₃] ₂ (4) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures have been determined for each of the four compounds. Compound 1 exists in the form of two symmetrically independent molecules in the crystalline state due to differences in their similar torsion angles. In all of the four structures there are intramolecular -Sn-Cl?H-N- hydrogen bonds, in addition to weak C-H?O and C-H?Cl hydrogen bonds. Both ¹H and ¹³C NMR spectra show the coupling of ^119/117Sn nuclei with methyl proton and carbon atoms. The δ(³¹P) of these complexes are in upfields with respect to their corresponding reported ligands. The spectroscopic and structural properties of these complexes were compared with those corresponding ligands.

Full text of DOI:10.1016/j.jorganchem.2006.06.032

Journal of Organometallic Chemistry 691 (2006) 4215–4224
www.elsevier.com/locate/jorganchem
Two conformers in the solid state for a novel organotin(IV) complex
of a phosphoramidate: Syntheses, spectroscopic study and
crystal structures of several new organotin(IV) complexes of
N-benzoylphosphoric triamides
*
Khodayar Gholivand , Zahra Shariatinia
Department of Chemistry, Tarbiat Modarres University, Gish Bridge, Jalal al Ahmad Highway, P.O. Box 14115-175, Tehran, Iran
Received 11 April 2006; received in revised form 4 June 2006; accepted 8 June 2006
Available online 4 July 2006
Abstract
Several novel organotin(IV) complexes with formula SnCl2(CH3)2(X)2, X = C6H5C(O)NHP(O)(NC4H8)2 (1), C6H5C(O)NH-
P(O)(NC5H10)2 (2), C6H5C(O)NHP(O)[N(CH3)(C6H11)]2 (3), C6H5C(O)NHP(O)[NH-C(CH3)3]2 (4) were synthesized and characterized
1
by H, 13C, 31P NMR, IR spectroscopy and elemental analysis. The structures have been determined for each of the four compounds.
Compound 1 exists in the form of two symmetrically independent molecules in the crystalline state due to differences in their similar
torsion angles. In all of the four structures there are intramolecular –Sn–Clꢀ ꢀ ꢀH–N– hydrogen bonds, in addition to weak C–Hꢀ ꢀ ꢀO
1
and C–Hꢀ ꢀ ꢀCl hydrogen bonds. Both H and 13C NMR spectra show the coupling of 119/117Sn nuclei with methyl proton and carbon
atoms. The d(31P) of these complexes are in upfields with respect to their corresponding reported ligands. The spectroscopic and struc-
tural properties of these complexes were compared with those corresponding ligands.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Organotin(IV) complexes; NMR spectroscopy; X-ray crystallography
1. Introduction
tion environment for the central tin atom [8]. The Sn(IV)
atoms in organotin(IV) complexes of O-donor ligands,
such as phosphoramidates [9], imidodiphosphonic acids
[10] and bis(diphenylphosphino)pyridine [11], exhibit a
hypervalent octahedral geometry, while in thiophosphi-
nates complexes [12] and some substituted dithiophosphate
stannocanes [13] indicate a trigonal-bipyramidal coordina-
tion. It has been reported the synthesis and crystal struc-
ture of a chiral bicyclic stannylated phosphoric triamide
in which the phosphoramide ligand act as a C-donor che-
late [14]. The NMR spectroscopic properties of some diorg-
anotin(IV) complexes with phosphates has been already
considered [15]. Herein, we focused on the synthetic, spec-
troscopic and crystal structure characteristics of four novel
diorganotin(IV) complexes with formula SnCl2(CH3)2(X)2,
X = C6H5C(O)NHP(O)(NC4H8)2 (1), C6H5C(O)NHP(O)-
(NC5H10)2 (2), C6H5C(O)NHP(O)[N(CH3)(C6H11)]2 (3),
Organotin(IV) complexes are an important part of orga-
nometallic chemistry because of their applications as bio-
cides like fungicides or antifouling agents [1], antitumor
[2] and antimicrobial [3] compounds. Nowadays, the
research on the preparation of different organotin(IV) com-
plexes with O- [4], N- [5], and C-donor [6] ligands becomes
a matter of great interest. Also, the preparation of stannyl-
platinum(IV) complexes in which the Sn(IV) atom adopts a
tetrahedral coordination is a noticeable branch of organo-
metallic chemistry [7]. Depending on the nature of different
substituents, these compounds indicate diverse coordina-
*
Corresponding author. Tel.: +98 21 8011001x3443; fax: +98 21
8006544.
E-mail address: gholi_kh@modares.ac.ir (K. Gholivand).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.06.032

4216
K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
C6H5C(O)NHP(O)[NH-C(CH3)3]2 (4) and their corre-
sponding reported ligands to discuss on their different
properties in solution and solid states. Compound 1 exists
as two symmetrically independent molecules in the crystal-
line lattice and we believe that, to our knowledge, this is the
first example for an organotin(IV) complex of a phospho-
ramidate with two conformers in the crystalline solid state.
constants with a value of about 3000.0 Hz in compounds
1 and 2 (containing cyclic aliphatic amine groups) and a
value of about 600.0 Hz in compounds 3 and 4 (containing
acyclic aliphatic amine moieties). The carbon atoms of
C@O groups in compounds 2–4 couple with their related
phosphorus atoms with 2J(P,C(O)) coupling constant
values from 1.9 Hz (4) to 2.5 Hz (2 and 3). The ipso carbon
atoms of phenyl rings in compounds 1–9 show 3J
(P,Caromatic) coupling constants in the range from 7.7 Hz
(9) to 8.8 Hz (2). 13C NMR spectra of compound 3 (con-
taining N-methylcyclohexyl groups) in both d6-DMSO
and CDCl3 solvents show seven signals for aliphatic carbon
atoms that five of them are doublet peaks. Therefore, the
two CH and CH2 groups of the two cyclohexyl rings (with
two and three bond distances from phosphorus atom) are
2. Results and discussion
2.1. NMR and IR study
Synthesis of complexes 1–4 were performed by the reac-
tion of dimethyltin(IV) dichloride with corresponding
phosphoric triamide ligands, Scheme 1. Some spectro-
scopic data of compounds 1–4 and their corresponding
ligands are listed in Table 1. 1H NMR spectra of molecules
1–4 show the Sn(IV) satellites with 2J(119Sn,H) and
2J(117Sn,H) coupling constants about 110.0 and 40.0 Hz
in d6-DMSO and about 90.0 and 40.0 Hz in CDCl3, respec-
tively. 13C NMR spectra reveal 1J(119/117Sn,C) coupling
2
not equivalent and we observe two J(P,C) coupling con-
3
stants (as well as two J(P,C) coupling constants). The N-
2
CH3 group indicates a J(P,C) coupling constants equal
to 4.2 Hz in d6-DMSO and 4.7 Hz in CDCl3. In our earlier
study, we reported two conformers in solution and solid
states for compound C6H5C(O)NHP(O)[NH-C(CH3)3]2
O
O
P
SnCl2(CH3)2
+
2
HN
X
X
X = aNC4H8
bNC5H10
(1),
(2),
cN(CH3)(C6H11) (3),
dNH-C(CH3)3
(4)
X
X
Cl
P
HN
O
CH3
Sn
Cl
O
O
H3C
O
NH
P
X
X
CH3
HN
N
CH3
N
d
c
b
a
NH
C
CH3
CH3
Scheme 1. Preparation pathway of organotin(IV) complexes 1–4.

K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
4217
1
(9) [16] which showed two series of signals in H, 13C and
31P NMR spectra due to the existence of two non-equiva-
lent tert-butyl groups. In compound 4, which is organo-
tin(IV) complex of ligand 9, we observe only one sets of
peaks and the two tert-butyl groups are equivalent. Thus,
it can be said that one of conformers with the two equal
tert-butyl groups is isolated from the solution to react with
SnCl2(CH3)2 and produced complex 4. 31P NMR spectra of
compounds 1 (with five-membered ring amine groups) and
2 (containing six-membered ring amine groups) indicate
that with increasing the ring size of amine groups, d(31P)
shifts to down fields (Table 1). The phosphorus-31 chemi-
cal shift of compound 5 with 4-fluorobenzoyl moiety
(10.33 ppm) is in upfield relative to its analogous com-
pound 2 (10.76 ppm). The d(31P) of compounds 1–4 are
in upfields with respect to their corresponding ligands,
Table 1. Therefore, complexation causes more shielding
of phosphorus atoms than those of the ligands.
IR spectra of compounds 1–4 show that the m(P@O) and
m(C@O) frequencies are in the range from 1153 cmꢁ1 (3) to
1115 cmꢁ1 (1) and 1679 cmꢁ1 (3) to 1648 cmꢁ1 (4), respec-
tively. The P@O stretching frequencies in complexes 1–4
are weaker than in those related ligands, but for C@O fre-
quencies opposite results were obtained (Table 1). The
P@O and C@O frequencies of analogous compounds 2
and 5 are close to each other. In complexes 1–4, the two
bands at about 550 and 510 cmꢁ1 are related to the asym-
metric and symmetric stretching frequencies of Sn–C bonds
[17], respectively, and the band at about 470 cmꢁ1 corre-
sponds to the vibration of Sn–O bond [18].
2.2. X-ray crystallography investigation
Single crystals of compounds 1–4 were obtained from a
solution of methanol and acetonitrile after slow evapora-
tion at room temperature. The crystal data and the details
of the X-ray analysis are given in Table 2, selected bond
lengths and bond angles in Tables 3 and 4 and hydrogen
bonding data in Table 5. Molecular structures of these
compounds are shown in Figs. 1–5. Complex 1 exists as
two crystallographically independent molecules (1 and 10)
in the crystalline lattice due to the differences in similar tor-
sion angles of these two independent molecules (Figs. 1
and 2) and we found that this is the first organotin(IV) com-
plex of a phosphoramidate with two conformers in the crys-
talline state. The torsion angles Sn(1)–O(1)–P(1)–N(1) and
Sn(10)–O(10)–P(10)–N(10) (1 and 10) are ꢁ54.5(3)ꢁ and
ꢁ55.1(3)ꢁ, respectively (also compare the torsion angles
O(1)–P(1)–N(2)–C(8), O(1)–P(1)–N(2)–C(11) (1) with
O(10)–P(10)–N(20)–C(80), O(10)–P(10)–N(20)–C(110) (10) that
are ꢁ121.3(3)ꢁ, 53.5(3)ꢁ and 51.6(3)ꢁ, ꢁ122.8(3)ꢁ). In each
conformer of this compound, the two aliphatic rings of pyr-
rolidine groups have puckered shape and they are not pla-
nar. The C(13D), C(14D) and C(14A) carbon atoms
and some hydrogen atoms of one pyrrolidinyl ring in each
of the conformers 1 and 10 show disorder in the crystal.
Similarly, the crystal structure of the corresponding ligand

4218
K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
Table 2
Crystallographic data for complexes 1–4
Compound
1
2
3
4
Empirical formula
Formula weight
Temperature (K)
C32H50Cl2N6O4P2Sn
834.31
120(2)
C36H58Cl2N6O4P2Sn
890.41
120(2)
C44H74Cl2N6O4P2Sn
1002.62
120(2)
C32H58Cl2N6O4P2Sn
842.37
200(2)
˚
Wavelength (A)
0.7173
0.7173
0.7173
0.7173
Crystal system
Space group
Unit cell dimensions
Triclinic
Monoclinic
P21/c
Triclinic
Triclinic
Triclinic, P1
ꢀ
ꢀ
ꢀ
P1
P1
˚
a (A)
9.3670(6)
15.716(2)
8.6542(12)
16.517(3)
8.8856(19)
10.888(2)
14.064(3)
72.902(5)
88.69(17)
68.160(6)
1201.4(4)
1
1.386
0.756
526
0.3 · 0.3 · 0.2
2.12–27.99
ꢁ11 6 h 6 11,
ꢁ14 6 k 6 14,
ꢁ18 6 l 6 18
12425/5796 (0.0375)
9.283(8)
˚
b (A)
15.0510(9)
15.3223(9)
61.7326(11)
90.1137(12)
88.5574(13)
1901.7(2)
10.298(7)
12.319(10)
66.47(5)
71.69(6)
89.38(6)
1016.1(14)
1
1.377
0.880
438
0.15 · 0.15 · 0.15
1.92–28.00
ꢁ12 6 h 6 12,
ꢁ13 6 k 6 13,
ꢁ15 6 l 6 16
5169/4875 (0.0155)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
111.688(3)
3
˚
V (A )
2087.4(5)
2
1.417
0.861
924
0.4 · 0.2 · 0.2
2.65–29.00
ꢁ21 6 h 6 15,
ꢁ10 6 k 6 11,
ꢁ22 6 l 6 20
12293/5492 (0.0656)
Z
2
Dcalc (Mg mꢁ3
)
1.457
0.939
860
0.2 · 0.3 · 0.2
1.51–27.50
ꢁ12 6 h 6 10,
ꢁ19 6 k 6 17,
ꢁ19 6 l 6 19
14756/8578 (0.0356)
Absorption coefficient (mmꢁ1
F(000)
)
Crystal size (mm3)
h Range for data collection (ꢁ)
Limiting indices
Reflections collected/unique
(Rint
)
Completeness to h (%)
98.1
98.7
99.6
99.2
Absorption correction
Semi-empirical from
equivalents
Semi-empirical from
equivalents
Semi-empirical from
equivalents
None
Maximum and minimum
transmission
0.8344 and 0.762
0.8467 and 0.7246
0.861 and 0.793
0.861 and 0.793
Refinement method
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
8578/3/456
0.964
5492/66/234
1.072
5796/0/270
1.032
4875/0/220
1.021
R1 = 0.0451,
wR2 = 0.0869
R1 = 0.0649,
wR2 = 0.0908
2.348 and ꢁ1.029
R1 = 0.0536,
wR2 = 0.1049
R1 = 0.0837,
wR2 = 0.1165
2.461 and ꢁ1.091
R1 = 0.0424,
wR2 = 0.1001
R1 = 0.0558,
wR2 = 0.1076
0.958 and ꢁ0.757
R1 = 0.0351,
wR2 = 0.0909
R1 = 0.0355,
wR2 = 0.0912
1.140 and ꢁ1.423
R indices (all data)
Largest difference in peak and
ꢁ3
˚
hole (e A
)
of 1 (C6H5C(O)NHP(O)(NC4H8)2) showed two conform-
ers in the solid state [19] and both of them had disorder
in their structures.
The data of hydrogen bonding in these structures are pre-
sented in Table 5. In each independent molecule of com-
pound 1, intramolecular –Sn–Clꢀ ꢀ ꢀH–N– hydrogen bonds
were formed. Considering weak intermolecular C–Hꢀ ꢀ ꢀCl
and C–Hꢀ ꢀ ꢀO hydrogen bonds leads to a three-dimensional
polymeric cluster in the lattice. This is observed in the struc-
tures 2 and 3, but in 3 a two-dimensional polymeric chain was
obtained (Fig. 6). In the crystalline network of 4, there are
intramolecular –Sn–Clꢀ ꢀ ꢀH–N– hydrogen bonds plus inter-
molecular N(3)–H(3B)ꢀ ꢀ ꢀO(1) hydrogen bond that produced
continuous dimmers leading to a polymeric chain. Also, the
intramolecular N(2)–H(2A)ꢀ ꢀ ꢀO(1) hydrogen bond was
observed in this structure. These hydrogen bonds besides
weak C–Hꢀ ꢀ ꢀCl and C–Hꢀ ꢀ ꢀO hydrogen bonds produced a
two-dimensional cluster. In previously reported organo-
tin(IV) complex, [4-F-C6H4C(O)NHP(O)(NC5H10)2]2-
SnCl2(CH3)2 [9], only weak intermolecular C–Hꢀ ꢀ ꢀCl
hydrogen bonds (intramolecular –Sn–Clꢀ ꢀ ꢀH–N– hydrogen
bonds were present) formed a two-dimensional polymer.
The corresponding ligand of complex 2 (C6H5C(O)NHP-
(O)(NC5H10)2) consists of four independent molecules in
the crystalline network (due to the differences in similar tor-
sion angles of these four independent molecules) [20], but in
the case of 2 we observe only one molecule in the lattice,
Fig. 3. Compound 3 as well as its corresponding ligand indi-
cate a symmetric molecule in the crystalline state (Fig. 4). In
the structure of compound 4, the C(90), C(100) and C(110)
atoms and their related hydrogen atoms of tert-butyl group
indicate disorder (Fig. 5). The structure of corresponding
ligand of 4 (C6H5C(O)NHP(O)[NH-C(CH3)3]2) showed
two conformers in solution and solid state that was con-
firmed by NMR and X-ray crystallography [16]. In struc-
tures 1, 10 and 4 due to the existence of disorder in the
molecules the structures are asymmetric but in compounds
2 and 3 the structures are symmetric.

K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
4219
Table 3
˚
Selected bond lengths (A) and angles (ꢁ) for compounds 1 and 2
Compound 1
Compound 2
Sn(1)–C(1M)
Sn(1)–O(1)
Sn(1)–Cl(1)
P(1)–O(1)
P(1)–N(2)
P(1)–N(3)
2.100(4)
2.212(2)
2.5846(10)
1.519(3)
1.610(3)
1.615(3)
1.680(3)
1.220(4)
2.113(4)
2.203(2)
2.5768(10)
1.516(3)
1.687(3)
1.617(3)
1.608(3)
1.218(4)
Sn(1)–C(1M)
Sn(1)–O(1)
Sn(1)–Cl(1)
O(1)–P(1)
O(2)–C(1)
N(1)–C(1)
N(1)–P(1)
N(1)–H(1N)
N(2)–C(8)
N(2)–C(12)
N(2)–P(1)
N(3)–C(13)
N(3)–C(17)
N(3)–P(1)
C(1)–C(2)
C(2)–C(3)
2.111(4)
2.223(2)
2.5658(8)
1.505(3)
1.218(4)
1.390(4)
1.689(3)
0.8585
1.469(5)
1.482(5)
1.626(3)
1.474(4)
1.480(4)
1.627(3)
1.502(5)
1.388(5)
P(1)–N(1)
O(2)–C(1)
Sn(10)–C(1M0)
Sn(10)–O(10)
Sn(10)–Cl(10)
O(10)–P(10)
N(10)–P(10)
N(20)–P(10)
N(30)–P(10)
O(20)–C(70)
C(1M)–Sn(1)–C(1M)#1
C(1M)–Sn(1)–O(1)
C(1M)#1–Sn(1)–O(1)
O(1)–Sn(1)–O(1)#1
O(1)–Sn(1)–Cl(1)#1
C(1M)–Sn(1)–Cl(1)
C(1M)#1–Sn(1)–Cl(1)
O(1)–Sn(1)–Cl(1)
Cl(1)–Sn(1)–Cl(1)#1
O(1)–P(1)–N(2)
O(1)–P(1)–N(3)
N(2)–P(1)–N(3)
O(1)–P(1)–N(1)
180.000(1)
88.31(13)
91.69(13)
180.000(1)
88.76(7)
89.60(12)
90.40(12)
91.24(7)
C(1M)–Sn(1)–C(1M)#1
C(1M)–Sn(1)–O(1)
C(1M)#1–Sn(1)–O(1)
O(1)–Sn(1)–O(1)#1
O(1)#1–Sn(1)–Cl(1)#1
C(1M)–Sn(1)–Cl(1)
C(1M)#1–Sn(1)–Cl(1)
O(1)–Sn(1)–Cl(1)
O(1)#1–Sn(1)–Cl(1)
Cl(1)#1–Sn(1)–Cl(1)
P(1)–O(1)–Sn(1)
O(1)–P(1)–N(3)
O(1)–P(1)–N(2)
180.0
87.21(13)
92.79(13)
180.00(11)
88.16(7)
89.49(10)
90.51(10)
88.16(7)
91.84(7)
180.0
144.41(15)
109.47(15)
117.54(16)
106.40(16)
104.11(15)
115.07(17)
104.52(16)
126.7(3)
129.5
180.0
116.35(16)
107.35(16)
107.57(17)
105.61(15)
105.86(16)
114.36(16)
180.000(2)
91.86(13)
88.14(13)
180.000(1)
89.84(13)
90.16(13)
89.12(7)
N(2)–P(1)–N(1)
N(3)–P(1)–N(1)
N(3)–P(1)–N(2)
O(1)–P(1)–N(1)
N(3)–P(1)–N(1)
N(2)–P(1)–N(1)
C(1M0)–Sn(10)–C(1M0)#2
C(1M0)–Sn(10)–O(10)#2
C(1M0)–Sn(10)–O(10)
O(10)#2–Sn(10)–O(10)
C(1M0)–Sn(10)–Cl(10)
C(1M0)#2–Sn(10)–Cl(10)
O(10)#2–Sn(10)–Cl(10)
O(10)#1–Sn(10)–Cl(10)
O(10)#1–Sn(10)–Cl(10)#2
Cl(10)–Sn(10)–Cl(10)#2
P(10)–O(10)–Sn(10)
O(10)–P(10)–N(30)
C(1)–N(1)–P(1)
C(1)–N(1)–H(1N)
P(1)–N(1)–H(1N)
C(8)–N(2)–C(12)
C(8)–N(2)–P(1)
C(12)–N(2)–P(1)
C(13)–N(3)–C(17)
C(13)–N(3)–P(1)
C(17)–N(3)–P(1)
Sn(1)–C(1M)–H(1MA)
Sn(1)–C(1M)–H(1MB)
H(1MA)–C(1M)–H(1MB)
Sn(1)–C(1M)–H(1MC)
H(1MA)–C(1M)–H(1MC)
H(1MB)–C(1M)–H(1MC)
100.9
111.4(3)
124.3(3)
120.8(2)
113.2(3)
123.7(2)
123.0(3)
109.5
109.5
109.5
109.5
109.5
90.88(7)
89.12(7)
180.000(1)
140.18(15)
107.42(16)
116.00(17)
107.74(16)
105.47(14)
114.62(17)
105.87(16)
O(10)–P(10)–N(20)
N(30)–P(10)–N(20)
O(10)–P(10)–N(10)
N(30)–P(10)–N(10)
N(20)–P(10)–N(10)
109.5
˚
In molecules 1–4, like their related phosphoric triamide
ligands, the phosphoryl and the carbonyl groups are anti.
The phosphorus atoms in these structures have slightly
distorted tetrahedral configuration. The bond angles
around P(1) atoms in these compounds are in the range
from 117.77(14)ꢁ (3) to 103.62(11)ꢁ (4), for the angles
O(1)–P(1)–N(2) and N(2)–P(1)–N(1), respectively. In these
compounds, the angles OPNamide (Namide is the nitrogen
atom of P(O)N(H)C(O) moiety) are lower than the angles
OPNamine (Namine is the nitrogen atom of P(O)NR moi-
ety). The P@O bond lengths in molecules 1–4, are
[1.519(3), 1.516(3)], 1.505(3), 1.496(2) and 1.493(2) A that
˚
are larger than the normal P@O bond length (1.45 A)
[21]. The P@O bond lengths in complexes 1–4 are larger
than those of the corresponding ligands, Table 6. The
C@O bond length in compound 4 has the longest,
0
˚
˚
1.225(3) A, and in compounds 1 and 2, 1.218(4) A, has
the lowest value. A comparison between the two similar
compounds 2 and 5 revealed that the P@O and P–Namine
bond lengths in 2 is slightly longer than in 5, but the
C@O and P–Namide bond lengths show an opposite result,
Table 6.

4220
K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
Table 4
The P–Namide bond lengths are longer than the P–Namine
bond lengths, because of the resonance interaction of the
˚
Selected bond lengths (A) and angles (ꢁ) for compounds 3 and 4
Compound 3
Compound 4
N
amide with the C@O p system that cause a partial multiple
bond character in C–Namide (the C–Namide bond lengths are
shorter than the C–Namine bond lengths, Tables 3 and 4).
All of these P–N bonds are shorter than the typical P–N
Sn(1)–C(1)
Sn(1)–O(1)
Sn(1)–Cl(1)
P(1)–O(1)
P(1)–N(2)
P(1)–N(3)
P(1)–N(1)
O(2)–C(2)
N(1)–C(2)
N(1)–H(1)
N(2)–C(9)
N(2)–C(10)
N(3)–C(16)
N(3)–C(17)
2.111(3)
2.222(2)
2.5750(9) Sn(1)–Cl(1)
Sn(1)–C
Sn(1)–O(2)
2.105(3)
2.242(3)
2.570(2)
1.493(2)
1.617(2)
1.619(2)
1.689(2)
1.370(3)
0.8800
1.488(3)
0.8800
1.488(3)
0.8800
1.496(2)
1.625(3)
1.633(3)
1.692(3)
1.221(4)
1.378(4)
0.9521
1.476(4)
1.494(4)
1.462(4)
1.496(4)
P(1)–O(2)
P(1)–N(3)
P(1)–N(2)
P(1)–N(1)
N(1)–C(1)
N(1)–H(1A)
N(2)–C(8)
N(2)–H(2A)
N(3)–C(12)
N(3)–H(3B)
O(1)–C(1)
˚
single bond length (1.77 A) [21]. This is likely due to the
electrostatic effects (polar bonds) which overlap with P–N
r bond [22]. The environment of the nitrogen atoms is
practically planar. In compound 1 the angles C(8)–N(2)–
C(11), C(8)–N(2)–P(1) and C(11)–N(2)–P(1) are 110.8(3)ꢁ,
128.7(3)ꢁ and 120.4(3)ꢁ, respectively, with average
119.97ꢁ. The sum of surrounding angles around N(1) and
N(3) atoms are 359.2ꢁ and 357.0ꢁ,respectively. Similar
results were obtained for the nitrogen atoms of other struc-
tures that confirm the sp2 hybridization for the N atoms,
although due to the repulsion and steric interactions, some
angles are greater, and the others are smaller than 120ꢁ.
The central Sn atom in compounds 1–4 has octahedron
coordination. Identical ligands (the two methyl groups, the
two phosphoramidates and the two chlorine atoms) are in
trans positions with the bond angles of 180.0ꢁ around Sn
atom. The different ligands are cis to each other and C–
Sn–O, C–Sn–Cl and O–Sn–Cl bond angles are about 90ꢁ,
Tables 3 and 4. The Sn–C bond lengths in 1–4 are
1.225(3)
C(1)#1–Sn(1)–C(1)
C(1)#1–Sn(1)–O(1)
C(1)–Sn(1)–O(1)
O(1)–Sn(1)–O(1)#1
C(1)#1–Sn(1)–Cl(1)
C(1)–Sn(1)–Cl(1)
O(1)–Sn(1)–Cl(1)
O(1)#1–Sn(1)–Cl(1)
180.000(1)
90.58(11)
89.42(11)
180.000(1)
90.67(10)
89.33(10)
89.90(6)
C–Sn(1)–C#1
C–Sn(1)–O(2)
C#1–Sn(1)–O(2)
O(2)#1–Sn(1)–O(2)
O(2)#1–Sn(1)–Cl(1)#1
C–Sn(1)–Cl(1)
180.0
92.03(11)
87.97(11)
180.00(9)
88.23(8)
90.27(10)
89.73(10)
91.77(8)
180.0
110.88(13)
116.69(12)
108.71(13)
105.72(12)
110.90(13)
103.62(11)
142.66(11)
125.41(17)
117.3
117.3
128.78(17)
115.6
115.6
127.67(18)
116.2
116.2
109.5
109.5
109.5
C#1–Sn(1)–Cl(1)
O(2)#1–Sn(1)–Cl(1)
Cl(1)#1–Sn(1)–Cl(1)
O(2)–P(1)–N(3)
O(2)–P(1)–N(2)
N(3)–P(1)–N(2)
O(2)–P(1)–N(1)
N(3)–P(1)–N(1)
N(2)–P(1)–N(1)
P(1)–O(2)–Sn(1)
C(1)–N(1)–P(1)
C(1)–N(1)–H(1A)
P(1)–N(1)–H(1A)
C(8)–N(2)–P(1)
C(8)–N(2)–H(2A)
P(1)–N(2)–H(2A)
C(12)–N(3)–P(1)
C(12)–N(3)–H(3B)
P(1)–N(3)–H(3B)
Sn(1)–C–H(0A)
Sn(1)–C–H(0B)
H(0A)–C–H(0B)
Sn(1)–C–H(0C)
H(0A)–C–H(0C)
H(0B)–C–H(0C)
O(1)–C(1)–N(1)
90.10(6)
Cl(1)–Sn(1)–Cl(1)#1 180.00(3)
O(1)–P(1)–N(2)
O(1)–P(1)–N(3)
N(2)–P(1)–N(3)
O(1)–P(1)–N(1)
N(2)–P(1)–N(1)
N(3)–P(1)–N(1)
P(1)–O(1)–Sn(1)
C(2)–N(1)–P(1)
C(2)–N(1)–H(1)
P(1)–N(1)–H(1)
C(9)–N(2)–C(10)
C(9)–N(2)–P(1)
C(10)–N(2)–P(1)
C(16)–N(2)–C(17)
C(16)–N(3)–P(1)
C(17)–N(3)–P(1)
Sn(1)–C(1)–H(1A)
Sn(1)–C(1)–H(1B)
H(1A)–C(1)–H(1B)
Sn(1)–C(1)–H(1C)
H(1A)–C(1)–H(1C)
H(1B)–C(1)–H(1C)
O(2)–C(2)–N(1)
117.77(14)
108.00(13)
107.11(14)
104.84(13)
104.90(14)
114.51(13)
153.33(13)
125.2(2)
122.4
˚
[2.100(4), 2.113(4)], 2.111(4), 2.111(3) and 2.105(3) A,
respectively, that are quite close to those reported in the lit-
erature [23]. The Sn–Cl bond lengths in 1–4 are [2.5846(10),
˚
2.5768(10)], 2.5658(8), 2.5750(9) and 2.570(2) A lying in the
˚
normal covalent radii 2.37–2.60 A [24]. The Sn–O bond
lengths are [2.212(2), 2.203(2)], 2.223(2), 2.222(2) and
122.4
˚
116.0(3)
119.2(2)
120.3(2)
116.8(2)
122.2(2)
117.5(2)
109.5
109.5
109.5
109.5
109.5
2.242(3) A that are shorter than sum of the van der Waals
˚
radii of Sn and O atoms (3.70 A) [25].
3. Experimental
3.1. X-ray measurements
109.5
109.5
109.5
121.2(2)
X-ray data of compounds 1–3 were collected on a Bru-
ker SMART 1000 CCD area detector [26] and for com-
pound 4 on a Siemens P3/PC Siemens P3 four-circle
109.5
120.1(3)
Table 5
˚
Hydrogen bonds for complexes 1–4 (A and ꢁ)
˚
˚
˚
Compound
D–H–A
d(D–H) (A)
d(Hꢀ ꢀ ꢀA) (A)
\DHA (ꢁ)
d(Dꢀ ꢀ ꢀA) (A)
1
N(1)–H(1N)ꢀ ꢀ ꢀCl(1) [ꢁx, ꢁy + 1, ꢁz + 2]
0.94
0.97
2.51
2.45
152
153
3.370(5)
3.351(5)
N(10)–H(1N0)ꢀ ꢀ ꢀCl(10) [ꢁx + 1, ꢁy + 2, ꢁz + 1]
N(1)–H(1N)ꢀ ꢀ ꢀCl(1) [ꢁx, ꢁy + 1, ꢁz + 2]
N(1)–H(1)ꢀ ꢀ ꢀCl(1)
2
3
4
0.86
2.64
141
3.350(5)
3.294(3)
0.952
2.370
163.27
N(1)–H(1A)ꢀ ꢀ ꢀCl(1)
0.880
0.880
0.880
2.386
2.368
2.214
159.88
119.71
150.97
3.227
2.907
3.014
N(2)–H(2A)ꢀ ꢀ ꢀO(1)
N(3)–H(3B)ꢀ ꢀ ꢀO(1) [ꢁx + 1, ꢁy + 1, ꢁz]

K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
4221
Fig. 3. Molecular structure and atom labeling scheme for complex 2 (50%
probability ellipsoids).
Fig. 1. Molecular structure and atom labeling scheme for the two
independent molecules of complex 1 (50% probability ellipsoids).
Fig. 4. Molecular structure and atom labeling scheme for complex 3 (50%
probability ellipsoids).
diffractometer [27] with graphite-monochromated Mo Ka
˚
radiation (k = 0.71073 A). The structures were refined with
SHELXL-97 [28] by full-matrix least-squares on F2. The posi-
tions of hydrogen atoms were obtained from the difference
Fourier map. Routine Lorentz and polarization corrections
were applied and an absorption correction was performed
using the SADABS program for compounds 1–3 [29].
3.2. Spectroscopic measurements
1H, 13C and 31P NMR spectra were recorded on a Bru-
1
ker Avance DRS 500 spectrometer. H and 13C chemical
shifts were determined relative to internal TMS 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
Fig. 2. Two conformers of compound 1 in the crystalline lattice in which
the orientations of similar groups in the two molecules are different.

4222
K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
was evaporated to give a yellow powder. Recrystallization
in methanol–acetonitrile produced single crystals of 1 (yield
1
1.84 g, 35%). M.p. 167 ꢁC. H NMR (d6-DMSO): d 0.90–
1.12 [0.90 (d, 2J(119Sn,H) = 111.8 Hz), 0.97 (d,
2J(117Sn,H) = 43.7 Hz), 1.01 (s), 6H, CH3], 1.74 (quin,
3J(H,H) = 6.4 Hz,16H, 8CH2), 3.09–3.17 (m, 16H, 8CH2),
7.45 (t, 3J(H,H) = 7.6 Hz, 4H, Ar-H), 7.56 (t,
3
3J(H,H) = 7.6 Hz, 2H, Ar-H), 7.88 (d, J(H,H) = 7.6 Hz,
2
4H, Ar-H), 9.13 (d, J(PNH) = 6.6 Hz, 2H, NHamide). 13C
NMR (d6-DMSO):
d 168.14 (s, C@O), 133.90 (d,
3J(P,C) = 8.2 Hz), 132.02 (s), 128.27 (s), 128.14 (s), 45.89
(d, 2J(P,C) = 4.9 Hz), 25.87 (d, 3J(P,C) = 8.3 Hz), 22.34
1
(d, J(119/117Sn,C) = 2832.3 Hz). 31P NMR (d6-DMSO): d
6.85 (m). IR (KBr): m (cmꢁ1) = 3420 (w, NH), 3235 (m),
2865 (m), 1672 (s, C@O), 1444 (s), 1418 (s), 1249 (s),
1207 (s), 1115 (s, P@O), 1063 (s), 1014 (m), 864 (m, P–
N
amine), 837 (m), 702 (s, P–Namide), 577 (w, (Sn–C)as),
527 (m, (Sn–C)s), 480 (w, Sn–O). Anal. Calc. for
C32H50Cl2N6O4P2Sn: C, 46.07; H, 6.04; N, 10.07. Found:
C, 46.05; H, 6.03; N, 10.08%.
3.3.2. Bis(N-benzoyl, N0,N00-bis(pipperidinyl) phosphoric
triamide) dimethyl stannate(IV) dichloride (2)
N-Benzoyl, N0,N00-bis(pipperidinyl) phosphoric triamide
(3.35 g, 10 mmol) was added to a solution of dimethyl-
tin(IV) dichloride (1.10 g, 5 mmol) in methanol (40 mL)
and stirred at room temperature. After 16 days, the white
precipitate was filtered and 15 mL of acetonitrile was
added to the methanol solution. Single crystals of 2 were
obtained after 6 days (yield 3.77 g, 68%). M.p. 169 ꢁC.
Fig. 5. Molecular structure and atom labeling scheme for complex 4 (50%
probability ellipsoids).
1H NMR (d6-DMSO):
d
0.91–1.13 [0.91 (d,
2J(119Sn,H) = 112.4 Hz), 0.98 (d, 2J(117Sn,H) = 40.7 Hz),
1.02 (s), 6H, CH3], 1.74 (quin, 3J(H,H) = 6.4 Hz, 16H,
CH2), 3.09–3.17 (m, 16H, CH2), 7.45 (t, 3J(H,H) = 7.4 Hz,
3
4H, Ar-H), 7.56 (t, J(H,H) = 7.4 Hz, 2H, Ar-H), 7.88 (d,
3J(H,H) = 7.6 Hz, 4H, Ar-H), 8.43 (b, 1H, NHamide), 9.07
(d, 2J(PNH) = 6.1 Hz, 1H, NHamide). 13C NMR (d6-
3
DMSO): d 168.12 (s, C@O), 133.93 (d, J(P,C) = 8.3 Hz,),
Fig. 6. A two-dimensional polymer (tubular array) obtained from
intramolecular –Sn–Clꢀ ꢀ ꢀH–N– hydrogen bonds and weak intermolecular
C–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀCl in the crystalline network of 3.
131.98 (s), 128.24 (s), 128.11 (s), 44.98 (s), 25.79 (d,
3J(P,C) = 4.8 Hz), 22.15 (d, 1J(119/117Sn,C) = 2705.9 Hz).
1
31P NMR (d6-DMSO): d 10.17 (m). H NMR (CDCl3): d
1.18–1.36 [1.18 (d, 2J(119Sn,H) = 88.7 Hz), 1.23 (d,
2J(117Sn,H) = 41.1 Hz), 1.27 (s), 6H, CH3], 1.56 (m, 24H,
points were obtained with an Electrothermal instrument.
Ligands C6H5C(O)NHP(O)(NC4H8)2 [19], C6H5C(O)NH-
P(O)(NC5H10)2 [20], C6H5C(O)NHP(O)[N(CH3)(C6H11)]2
[30] and C6H5C(O)NHP(O)[NH-C(CH3)3]2 [16] for the
synthesis of complexes 1–4 were prepared as the literature
method.
3
CH2), 3.20 (m, 16H, CH2), 7.48 (t, J(H,H) = 7.5 Hz, 4H,
3
Ar-H), 7.57 (t, J(H,H) = 7.5 Hz, 2H, Ar-H), 7.87 (b, 1H,
3
NHamide), 7.95 (d, J(H,H) = 7.5 Hz, 4H, Ar-H), 8.69 (b,
1H, NHamide). 13C NMR (CDCl3):
d
167.11 (d,
2J(P,C) = 2.5 Hz, C@O), 132.48 (d, 3J(P,C) = 8.8 Hz,),
132.25 (s), 128.32 (s), 127.32 (s), 45.43 (d,
2J(P,C) = 3.2 Hz), 25.64 (d, 3J(P,C) = 4.8 Hz), 22.06 (d,
1J(119/117Sn,C) = 2767.9 Hz). 31P NMR (CDCl3): d 10.46
(m). IR (KBr): m (cmꢁ1) = 3250 (w, NH), 2930 (s), 1678
(s, C@O), 1444 (s), 1419 (s), 1337 (w), 1248 (m), 1162 (s),
1125 (s, P@O), 1073 (s), 959 (s), 860 (m), 838 (m, P–Namine),
721 (m, P–Namide), 559 (w, (Sn–C)as), 506 (w, (Sn–C)s), 471
(w, Sn–O). Anal. Calc. for C36H58Cl2N6O4P2Sn: C, 48.56;
H, 6.57; N, 9.44. Found: C, 48.54; H, 6.57; N, 9.43%.
3.3. Synthesis
3.3.1. Bis(N-benzoyl, N0,N00-bis(pyrrolidinyl) phosphoric
triamide) dimethyl stannate(IV) dichloride (1)
N-Benzoyl, N0,N00-bis(pyrrolidinyl) phosphoric triamide
(3.07 g, 10 mmol) was added to a solution of dimethyl-
tin(IV) dichloride (1.10 g, 5 mmol) in methanol (35 mL)
and stirred at room temperature. After 15 days, the solvent

K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
4223
Table 6
˚
P@O, P–Namide, P–Namine and C@O bond lengths (A) in compounds 1–9
No.
Compound
P@O
P–Namide
P–Namine
C@O
Reference
a
1
SnCl2(CH3)2[C6H5C(O)NHP(O)(NC4H8)2]2
1.519(3), 1.516(3)
1.680(3), 1.687(3)
1.610(3), 1.615(3),
1.617(3), 1.608(3)
1.626(3), 1.627(3)
1.625(3), 1.633(3)
1.619(2), 1.617(2)
1.220(4),
1.218(4)
1.218(4)
1.221(4)
1.225(3)
a
a
a
2
3
4
5
6
SnCl2(CH3)2[C6H5C(O)NHP(O)(NC5H10)2]2
SnCl2(CH3)2[C6H5C(O)NHP(O)[N(CH3)(C6H11)]2]2 1.496(2)
SnCl2(CH3)2[C6H5C(O)NHP(O)[NH-C(CH3)3]2]2
SnCl2(CH3)2[4-F-C6H4C(O)NHP(O)(NC5H10)2]2
C6H5C(O)NHP(O)(NC4H8)2
1.505(3)
1.689(3)
1.692(3)
1.689(2)
1.6921(17)
1.679(4)
1.493(2)
1.5012(14)
1.487(3)
1.6201(17), 1.6260(17) 1.222(2)
1.618(4), 1.615(4)
[9]
1.208(4), [19]
1.217(5)
7
C6H5C(O)NHP(O)(NC5H10 2
)
1.460(12), 1.472(13), 1.671(13), 1.661(13), 1.614(13), 1.642(14),
1.425(12), 1.463(11) 1.685(14), 1.690(13) 1.619(17), 1.631(14),
1.646(14), 1.589(15),
1.240(17), [20]
1.239(18),
1.228(18),
1.624(13), 1.603(15)
1.223(17)
8
9
C6H5C(O)NHP(O)[N(CH3)(C6H11)]2
C6H5C(O)NHP(O)[NH-C(CH3)3]2
1.4842(12)
1.473(2), 1.476(2)
1.6980(14)
1.711(2), 1.704(2)
1.6344(14), 1.6368(14) 1.218(2)
1.629(2), 1.629 (2),
1.619(3), 1.629 (2)
[30]
1.225(3), [16]
1.232(3)
a
This work.
3.3.3. Bis(N-benzoyl, N0,N00-bis(N-methylcyclohexyl)
phosphoric triamide) dimethyl stannate(IV) dichloride (3)
N-Benzoyl, N0,N00-bis(N-methylcyclohexyl) phosphoric
triamide (3.91 g, 10 mmol) was added to a solution of dim-
ethyltin(IV) dichloride (1.10 g, 5 mmol) in methanol
(45 mL) and stirred at room temperature. After 20 days,
the solvent was concentrated and 10 mL of acetonitrile
was added to the reaction vessel. The single crystals of 3
were obtained during 7 days by slow evaporation of the
IR (KBr): m (cmꢁ1) = 3425 (w, NH), 3205 (m), 2925 (s),
1679 (s, C@O), 1443 (s), 1418 (s), 1259 (m), 1153 (s,
P@O), 1001 (s), 968 (s), 886 (m), 847 (m, P–Namine), 707
(m, P–Namide), 563 (w, (Sn–C)as), 518 (w, (Sn–C)s), 489
(w, Sn–O). Anal. Calc. for C44H74Cl2N6O4P2Sn: C, 52.71;
H, 7.44; N, 8.38. Found: C, 52.70; H, 7.44; N, 8.36%.
3.3.4. Bis(N-benzoyl, N0,N00-bis(tert-butyl) phosphoric
triamide) dimethyl stannate(IV) dichloride (4)
1
solvents (yield 3.73 g, 61%). M.p. 183 ꢁC. H NMR (d6-
N-Benzoyl, N0,N00-bis(tert-butyl) phosphoric triamide
(3.11 g, 10 mmol) was added to a solution of dimethyl-
tin(IV) dichloride (1.10 g, 5 mmol) in methanol (30 mL)
and stirred at room temperature. After 5 days, the solvent
was evaporated and the white powder dissolved in metha-
nol/acetonitrile solution. After 7 days, single crystals of 4
DMSO): d 0.89–1.04 [0.89 (d, 2J(119Sn,H) = 109.8 Hz),
2
0.96 (d, J(117Sn,H) = 41.9 Hz), 1.00 (s), 6H, CH3], 1.12–
3
1.99 (m, 44H, CH, CH2), 2.53 (d, J(PNCH) = 10.8 Hz,
3
12H, CH3), 7.46 (t, J(H,H) = 7.3 Hz, 4H, Ar-H), 7.55 (t,
3
3J(H,H) = 7.3 Hz, 2H, Ar-H), 7.87 (d, J(H,H) = 7.3 Hz,
1
4H, Ar-H), 8.73 (b, 1H, NHamide), 9.04 (b, 1H, NHamide).
were obtained (yield 4.14 g, 78%). M.p. 235 ꢁC. H NMR
13C NMR (d6-DMSO): d 167.34 (d, 2J(P,C) = 2.0 Hz,
(d6-DMSO): d 0.91–1.13 [0.91 (d, J(119Sn,H) = 110.9 Hz),
2
3
C@O), 132.58 (d, J(P,C) = 8.2 Hz), 132.12 (s), 128.08 (s),
0.98 (d, 2J(117Sn,H) = 42.6 Hz), 1.02 (s), 6H, CH3], 1.21 (s,
127.44 (s), 56.72 (s), 54.20 (d, 2J(P,C) = 4.2 Hz, N-
CH3), 30.41 (d, 2J(P,C) = 3.9 Hz, CH), 30.26 (d,
36H, CH3), 4.00 (d, J(PNH) = 6.6 Hz, 4H, NH(amine)),
2
7.44 (t, 3J(H,H) = 7.6 Hz, 4H, Ar-H), 7.54 (t,
2
3
3J(P,C) = 2.2 Hz, CH2), 27.61 (d, J(P,C) = 4.1 Hz, CH),
3J(H,H) = 7.6 Hz, 2H, Ar-H), 7.95 (d, J(H,H) = 7.6 Hz,
25.74 (d, 3J(P,C) = 4.4 Hz, CH2), 25.15 (s), 24.72 (d,
4H, Ar-H), 9.46 (d, J(PNH) = 6.8 Hz, 2H, NHamide). 13C
2
1
2
1J(117Sn,C) = 566.4 Hz), 23.77 (d, J(119Sn,C) = 565.2 Hz).
NMR (d6-DMSO): d 168.15 (d, J(P,C) = 1.9 Hz, C@O),
1
3
31P NMR (d6-DMSO): d 13.60 (m). H NMR (CDCl3): d
134.07 (d, J(P,C) = 7.8 Hz), 131.79 (s), 128.01 (s), 127.93
2
1.02 (m, 4H), 1.17–1.35 [1.17 (d, J(119Sn,H) = 91.2 Hz),
(s), 50.32 (s), 31.21 (d, 3J(P,C) = 5.0 Hz), 22.42 (d,
1J(119/117Sn,C) = 586.5 Hz). 31P NMR (d6-DMSO): d 2.95
(m). IR (KBr): m (cmꢁ1) = 3315 (m, NH), 3155 (m), 2960
(m), 1648 (s, C@O), 1488 (m), 1447 (s), 1424 (s), 1389 (s),
1274 (w), 1219 (s), 1150 (s, P@O), 1046 (m), 1023 (m),
879 (w, P–Namine), 787 (m, P–Namide), 680 (w), 567 (w,
(Sn–C)as), 543 (w, (Sn–C)s), 479 (w, Sn–O). Anal. Calc.
for C32H58Cl2N6O4P2Sn: C, 45.62; H, 6.94; N, 9.98.
Found: C, 45.60; H, 6.93; N, 9.99%.
2
1.23 (d, J(117Sn,H) = 31.5 Hz), 1.26 (s), 6H, CH3], 1.47–
1.87 (m, 30H), 2.18 (m, 4H), 2.67 (d, 3J(PNCH) = 11.3 Hz,
3
12H, CH3), 3.40 (m, 4H), 7.47 (t, J(H,H) = 7.5 Hz, 4H,
Ar-H), 7.56 (t, 3J(H,H) = 7.5 Hz, 2H, Ar-H), 7.96 (d,
3J(H,H) = 7.5 Hz, 4H, Ar-H), 8.07 (b, 1H, NHamide), 9.30
(b, 1H, NHamide). 13C NMR (CDCl3): d 167.44 (d,
2J(P,C) = 2.5 Hz, C@O), 132.60 (d, 3J(P,C) = 8.6 Hz),
132.17 (s), 128.30 (s), 127.37 (s), 57.92 (s), 54.99 (d,
2J(P,C) = 4.7 Hz, N-CH3), 30.49 (d, 2J(P,C) = 3.6 Hz,
CH), 30.31 (d, 3J(P,C) = 2.1 Hz, CH2), 27.48 (d,
Acknowledgement
3
2J(P,C) = 5.6 Hz, CH), 25.53 (d, J(P,C) = 2.1 Hz, CH2),
25.02 (s), 24.32 (d, 1J(117Sn,C) = 615.9 Hz), 23.87 (d,
1J(119Sn,C) = 574.8 Hz). 31P NMR (CDCl3): d 14.02 (m).
Support of this work by Research Council of Tarbiat
Modarres University is gratefully acknowledged.

4224
K. Gholivand, Z. Shariatinia / Journal of Organometallic Chemistry 691 (2006) 4215–4224
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¨
Appendix A. Supplementary information
Crystallographic data for the structures 1–4 have been
deposited with Cambridge Crystallographic Data Center
as supplementary publication numbers CCDC 292741
(C32H50Cl2N6O4P2Sn1), CCDC 292742 (C36H58Cl2N6O4-
P2Sn1), CCDC 292743 (C44H74Cl2N6O4P2Sn1) and CCDC
286214 (C32H58Cl2N6O4P2Sn1). Copies of the data may be
obtained, free of charge, on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223
336 033; e-mail: deposit@ccdc.cam.ac.uk or www: www:
http://www.ccdc.cam.ac.uk). Supplementary data associ-
ated with this article can be found, in the online version,
at doi:10.1016/j.jorganchem.2006.06.032.
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