Syntheses, spectroscopic characterization and crystal structures of some new phosphoramidates and an organotin(IV) complex of N-(4-fluorobenzoyl)- N′,N″-bis(piperidinyl)phosphoric triamide

Article abstract of DOI:10.1016/j.poly.2005.07.035

Some new phosphoramidates with formula 4-F-C₆H ₄C(O)N(H)P(O)X₂, X = NC₄H₈ (1), NC₅H₁₀ (2), 4-CH₃-NC₅H₉ (3), NC₄H₈O (4), NC<

Full text of DOI:10.1016/j.poly.2005.07.035

Polyhedron 25 (2006) 711–721
www.elsevier.com/locate/poly
Syntheses, spectroscopic characterization and crystal structures
of some new phosphoramidates and an organotin(IV) complex of
N-(4-fluorobenzoyl)-N0,N00-bis(piperidinyl)phosphoric triamide
*
Khodayar Gholivand , Zahra Shariatinia, Mehrdad Pourayoubi
Department of Chemistry, Tarbiat Modarres University, Gisha Bridge, P.O. Box 14115-175, Tehran, Iran
Received 18 June 2005; accepted 25 July 2005
Available online 30 August 2005
Abstract
Some new phosphoramidates with formula 4-F-C6H4C(O)N(H)P(O)X2, X = NC4H8 (1), NC5H10 (2), 4-CH3-NC5H9 (3),
NC4H8O (4), NC6H12 (5), N(CH2CH3)2 (6), N(CH2CH2CH3)2 (7) were synthesized. The reaction of compound 2 with dimethyl-
tin(IV) dichloride leads to an octahedral organotin(IV) complex, SnCl2(CH3)2[4-F-C6H4C(O)N(H)P(O)(NC5H10)2]2 (8) with equal
ligands in trans positions. These compounds were characterized by IR, 1H, 13C, 31P, 119Sn NMR, mass spectroscopy and elemental
analysis. The structures have been determined for compounds 1, 2, 4, 5 and 8. Compound 2 exists as four symmetrically independent
molecules in the crystalline lattice. Compounds 1, 4 and 5 form dimmers via intermolecular –P@Oꢀ ꢀ ꢀH–N– hydrogen bonds that in 1
is centrosymmetric. In compound 2, two dimmers were formed; each of them was produced between two adjacent independent mol-
3
ecules. In compounds 1, 2, 3, 4 and 8, containing five- and six-membered ring amine groups, J(P,Caliphatic) > 2J(P,Caliphatic). Com-
pound 5 with seven-membered ring amine, similar to compounds 6 and 7 with acyclic aliphatic amines, shows that
2J(P,Caliphatic) > 3J(P,Caliphatic). Mass spectra of these compounds indicate the 4-F-C6H4CO+ and 4-F-C6H4CN+ fragments.
ꢀ 2005 Elsevier Ltd. All rights reserved.
Keywords: X-ray crystallography; NMR spectroscopy; Phosphoramidate; Organotin(IV) complex
1. Introduction
the organometallic compounds of tin(IV) are very
important antitumor agents [13,14]. Organotin(IV) com-
pounds have been extensively used as wood preserva-
tives, agrochemical fungicides and biocides [15,16].
The coordination compounds of organotin(IV) are a
matter of interest in recent researches [17–20]. In our
previous studies, we obtained some structures with two
conformers in the lattice [21–23]. Cain et al. reported
the crystal structure of compound {(5R,4S)-N-Pr-ephed-
rine}P(S)[NH(Si)(CH3)3] that has three independent
molecules in the unit cell [24]. The first phosphoramidate
with four crystallographically independent molecules
in the crystalline network was C6H5C(O)N(H)P(O)-
(NC5H10)2 [25] and in this work we report its analo-
gous compound 4-F-C6H4C(O)N(H)P(O)(NC5H10)2
(2). There are several articles that have been discussed
The chemistry of phosphoramidates is recently devel-
oped due to the biological activity [1–3] and also the
coordination chemistry [4–6] of these compounds. Some
of them with RCðOÞNðHÞPðOÞR12 formula were used as
O,O0-donor ligands for metal ions, particularly for rare
earth metal cations [7,8]. Although the crystal structures
of several phosphoramidates and their complexes are al-
ready known [4–6,9–12], there are little discussions
about the substituent effects on the structural and
NMR parameters. Among coordination compounds,
*
Corresponding author. Tel. +98 21 8011001x3443; fax: +98 21
8006544.
E-mail address: gholi_kh@modares.ac.ir (K. Gholivand).
0277-5387/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.07.035

712
K. Gholivand et al. / Polyhedron 25 (2006) 711–721
on noticeable information on the coupling constants be-
tween 31P and 13C (or 1H) nuclei [26,27]. Herein, we rep-
resent the synthesis of some new phosphoramidates with
general formula 4-F-C6H4C(O)N(H)P(O)X2, X =
NC4H8 (1), NC5H10 (2), 4-NC5H9-CH3 (3), NC4H8O
(4), NC6H12 (5), N(CH2CH3)2 (6), N(CH2CH2CH3)2
(7). Also, we studied the behavior of 2 as O-donor ligand
to interaction with SnCl2(CH3)2 and an octahedral
organotin(IV) complex, SnCl2(CH3)2[4-F-C6H4C(O)-
N(H)P(O)(NC5H10)2]2 (8) was prepared. The structures
of compounds 1, 2, 4, 5 and 8 were determined by
X-ray crystallography. Furthermore, we discussed on
structural, NMR and Mass spectral parameters in these
compounds and their analogous derivatives.
C6H4C(O)NHP(O)Cl2 was prepared according to the lit-
erature method [32].
2.4. Syntheses
2.4.1. General procedure for synthesis of compounds 1–8
Compounds 1–7 were prepared by the reaction of 10
mmol N-(4-fluorobenzoyl) phosphoramidic dichloride
with 40 mmol of corresponding amines in dry chloro-
form and stirred at ꢂ5 ꢁC. After about 5 h, the solvent
was removed and product was washed with H2O and
recrystallized from methanol/chloroform. Compound 8
was synthesized by the reaction of 20 mmol of 2 with
10 mmol dimethyltin(IV) dichloride in methanol at
room temperature.
2. Experimental
3. Results and discussion
2.1. Materials
3.1. NMR and IR study
Dipropylamine (P99%), morpholine (>98%) (Merck)
and 4-fluorobenzamide (98%), formic acid (98%), phos-
phorus pentachloride (P98%), pyrrolidine (>98%),
piperidine (P99.5%), hexemethyleneimine (P97%),
diethylamine (P99.7%), dimethyltin dichloride (ꢁ95%)
(Fluka) were used as supplied. In all reactions, the low
temperature condition was used.
Synthesis of compounds 1–7 were performed by the
reaction of N-(4-fluorobenzoyl) phosphoramidic dichlo-
ride [32] with corresponding amines, Scheme 1. Com-
pound 8 was obtained from the reaction of compound
2 with dimethyltin(IV) dichloride. 13C NMR spectra of
compounds 1, 2, 3, 4 and 8, containing five- and six-
3
membered ring amine groups, show that J(P,Caliphatic
)
2
is greater than J(P,Caliphatic). For compound 5 with se-
ven-membered ring amine, similar to compounds 6 and
2.2. X-ray measurements
7
with acyclic aliphatic amines, 2J(P,Caliphatic) >
X-ray data of compounds 1, 2, 5 and 8 were collected
on a Bruker SMART 1000 CCD [28] and for compound
4 on a Siemens P3/PC [29] single crystal diffractometer
with graphite monochromated Mo Ka radiation
3J(P,Caliphatic). Compound 6 shows an opposite result
for 2,3J(P,Caliphatic) relative to compound 1 (with diethyl-
amine group), Scheme 2. Also, it is observed from Table 1
that with increasing the ring size of amine groups in
compounds 1–5, the 3J(P,Caliphatic) becomes smaller
and it varies from 8.0 Hz in 1 to 3.8 Hz in 5. These re-
sults are in good agreement with our previous studies
on the similar compounds 9–12, Table 1. The carbon
atoms of C@O groups in compounds 6, 7, 8 and 10 cou-
ple with their related phosphorus atoms with 2J(P,C(O))
coupling constant values in the range from 1.9 Hz in 6
and 8 to 3.9 Hz in 10. The ipso carbon atoms of phenyl
˚
(k = 0.71073 A). The structures were refined with
SHELXL-97 [30] by full-matrix least-squares on F2. The
positions of hydrogen atoms were obtained from the dif-
ference Fourier map. Routine Lorentz and polarization
corrections were applied and an absorption correction
was performed using the SADABS program [31].
2.3. Spectroscopic measurements
3
rings in compounds 1–12 show J(P,Caromatic) coupling
All reactions were performed under argon atmo-
sphere and in dry solvents. 1H, 13C, 31P and 119Sn
NMR spectra were recorded on a Bruker Avance DRS
500 spectrometer. 1H and 13C chemical shifts were deter-
mined relative to internal TMS, 31P chemical shifts rela-
tive to 85% H3PO4 as external standard and 119Sn
chemical shift relative to Sn(CH3)4 solution. Infrared
(IR) spectra were recorded on a shimadzu model IR-60
spectrometer. Elemental analysis was performed
using a Heraeus CHN-O-RAPID apparatus. High reso-
lution mass spectra were obtained with a Shimadzu
model QP-1100EX spectrometer (EI, 70 eV). 4-F-
constants in the range from 7.6 Hz in 3 to 8.9 Hz in 6
and 7.
13C NMR spectrum of compound 3 indicates eight
peaks for the two unequivalent aliphatic rings of
4-methylpiperidinyl groups. The four doublet signals
with two various 2J(P,Caliphatic) [and also 3J(P,Caliphatic)]
coupling constant values are related to the carbon atoms
with two and three bond distances from phosphorus
atom, Table 1 and Fig. 1.
The d (31P) of compounds 1, 2 and 5 indicates that
with increasing the ring size of amine groups, it shifts
to down fields (Table 1). The phosphorus-31 chemical

K. Gholivand et al. / Polyhedron 25 (2006) 711–721
713
O
C
O
P
+
4 HR
N
H
Cl
Cl
R = aNC4H8
bNC5H10
(1)
(2)
F
c4-CH3-NC5H 9 (3)
dNC4H8O
eNC6H1 2
N(C2H5)2
N(C3H7)2
(4)
(5)
(6)
(7)
O
C
O
P
+
2 Cl H2R
N
R
H
R
F
a
b
e
c
d
N
N
H3C
N
O
N
N
Scheme 1. Preparation of compounds 1–7.
O
P
O
P
N
N
N
N
NH
NH
R
R
1
6
O
O
P
P
N
N
N
N
NH
NH
R
R
5
7
Scheme 2. The formula of compounds 1, 5–7.
shifts of compounds 1, 2 and 5 with 4-fluorobenzoyl
moiety are in upfields relative to their analogous com-
pounds 10–12 with formula C6H5C(O)N(H)P(O)R2
(R = NC4H8, NC5H10, NC6H12). The d (31P) of com-
pounds 2 and its organotin(IV) complex, 8, are close
to each other, 10.34 ppm in 2 and 10.15 ppm in 8.
119Sn NMR of compound 8 shows a signal at ꢂ210.75
of two ligands. The fluorine substituent couple with aro-
matic carbon and proton atoms of phenyl ring and we
observed 1–4J(F,Caromatic) and 4J(F,Haromatic) in com-
pounds 1–8.
IR spectra of compounds 1–8 show that the mP@O
;
mP–N(amine); mP–N(amide) and mC@O frequencies are in the
range from 1162 in 8 to 1215 in 1; 870 in 1 to 964 in
4; 752 (1) to 757 (5 & 8) and 1661 (5) to 1680 (8), respec-
tively. The C@O frequency in structurally similar com-
1
ppm for the Sn atom. H NMR spectrum of this mole-
cule indicates two separate signals for the NH protons

714
K. Gholivand et al. / Polyhedron 25 (2006) 711–721
Table 1
2J(P,Caliphatic), 3J(P,Caliphatic) and 3J(P,Caromatic) (Hz), d(31P) (ppm) for compounds 1–12 and m.p. (ꢁC), yield (%) of 1–8
No. Compound
2J(P,Caliphatic
)
3J(P,Caliphatic
)
3J(P,Caromatic
)
d(31P) M.p. (ꢁC) Yield (%)
1
2
4-F-C6H4CðOÞNðHÞPðOÞR21
5.0 (CH2)
0.0 (CH2)
8.0 (CH2)
4.8 (CH2)
8.5
8.7
7.05 181
10.34 194
10.39 189
9.44 193
12.72 144
12.92 126
88
83
79
70
68
73
82
31
4-F-C6H4CðOÞNðHÞPðOÞR22
4-F-C6H4CðOÞNðHÞPðOÞR23
4-F-C6H4CðOÞNðHÞPðOÞR24
4-F-C6H4CðOÞNðHÞPðOÞR25
4-F-C6H4C(O)N(H)P(O)[N(C2H5)2]2
4-F-C6H4C(O)N(H)P(O)[N(C3H7)2]2
3
3.4 (CH2), 1.9 (CH2) 5.8 (CH2), 4.8 (CH2) 7.6
0.0 (CH2)
4.5 (CH2)
1.9 (C@O), 5.0 (CH2) 0.0 (CH3)
2.4 (C@O), 4.5 (CH2) 2.3 (CH2)
4
5.4 (CH2)
3.8 (CH2)
8.6
8.7
8.9
8.9
8.1
8.7
8.5
5
6
7
13.44
81
8
9a
SnðCH3Þ2Cl2½4-F-C6H4CðOÞNðHÞPðOÞR22ꢃ2 1.9 (C@O), 2.6 (CH2) 4.9 (CH2)
10.15 176
8.84
12.02
12.04
14.70
C6H5CðOÞNðHÞPðOÞR21
5.5 (CH2)
3.9 (C@O), 2.7 (CH2) 4.7 (CH2)
2.9 (CH2), 0.0 (CH2) 4.9 (CH2), 5.1 (CH2) 8.6
4.7 (CH2)
8.6 (CH2)
10b C6H5CðOÞNðHÞPðOÞR22
11b C6H5CðOÞNðHÞPðOÞR32
12c C6H5CðOÞNðHÞPðOÞR52
4.2 (CH2)
8.7
R5
R2
R3
R4
R1
N
N
H3C
N
O
N
N
.
a
The data of this compound are given in [23].
The data of these compounds are given in [25].
The data of this compound are given in [42].
b
c
Fig. 1. Selected region of 13C NMR spectrum of compound 3.

Table 2
Crystallographic data for 1, 2 and 4
1
2
4
Empirical formula
Formula weight
T (K)
C
325.32
120(2)
0.71073
monoclinic
P21/n
15H21FN3O2P
C17H25FN3O2P
353.37
120(2)
0.71073
triclinic
C15H21FN3O4P
357.32
293(2)
0.71073
monoclinic
C2/c
˚
k (A)
Crystal system
Space group
Unit cell dimensions
ꢀ
P1
˚
a (A)
9.4043(19)
9.4800(11)
15.732(3)
˚
b (A)
9.4365(19)
17.744(4)
17.5062(19)
22.439(2)
10.740(2)
21.553(4)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
90.044(4)
90
1574.6(6)
76.168(2)
84.962(3)
84.366(3)
3590.4(7)
90
106.93(3)
90
3
˚
V (A )
3483.9(12)
Z
4
8
8
Dcalc (Mg mꢂ3
)
1.372
0.196
688
0.4 · 0.5 · 0.6
1.307
0.177
1504
0.3 · 0.2 · 0.2
1.362
0.192
1504
0.4 · 0.36 · 0.32
3.30–28.06
0 6 h 6 20, 0 6 k 6 14, ꢂ28 6 l 6 27
4311/4165 (0.0092)
(h = 28.06ꢁ) 98.2
none
Absorption coefficient (mmꢂ1
F(000)
Crystal size (mm3)
h Range for data collection (ꢁ)
Limiting indices
Reflections collected/unique (Rint
Completeness to h (%)
Absorption correction
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
)
2.30–28.99
0.94–26.00
ꢂ12 6 h 6 12, ꢂ12 6 k 6 12, ꢂ20 6 l 6 24
13097/4107 (0.0307)
(h = 28.99ꢁ) 98.0
none
0.928 and 0.197
full-matrix least-squares on F2
4107/0/199
ꢂ11 6 h 6 11, ꢂ21 6 k 6 21, ꢂ27 6 l 6 27
25752/13810 (0.0412)
(h = 26.00ꢁ) 97.7
semi-empirical from equivalents
0.9654 and 0.9487
full-matrix least-squares on F2
13810/12/857
)
full-matrix least-squares on F2
4165/0/253
1.000
1.020
1.025
R1 = 0.0410, wR2 = 0.1093
R1 = 0.0451, wR2 = 0.1143
0.957 and ꢂ0.329
R1 = 0.0698, wR2 = 0.1490
R1 = 0.1258, wR2 = 0.1705
0.654 and ꢂ0.516
R1 = 0.0488, wR2 = 0.1178
R1 = 0.0765, wR2 = 0.1346
0.251 and ꢂ0.228
R indices (all data)
Largest difference in peak and hole (e A
ꢂ3
˚
)

716
K. Gholivand et al. / Polyhedron 25 (2006) 711–721
pounds 1, 6 and also in 5, 7 (see Scheme 2) are very close
to each other. The P@O stretching frequency in complex
8 (1162 cmꢂ1) is weaker than in its ligand 2 (1178 cmꢂ1),
but for C@O frequency an opposite result was obtained
(1680 cmꢂ1 in 8 and 1668 cmꢂ1 in 2). The two bands at
542 and 511 cmꢂ1 are related to the asymmetric and
symmetric stretching frequencies of Sn–C bonds, respec-
tively [33] and the band at 467 cmꢂ1 corresponds to the
vibration of Sn–O bond [34].
crystal lattice. This is due to the differences in similar
torsion angles of these four independent molecules. This
phenomenon was also observed for compound
C6H5C(O)N(H)P(O)(NC5H10)2 [25]. The complexation
of compound 2 with dimethyltin dichloride (compound
8) produced a coordination compound with two
symmetrically equal phosphoramidate ligands, Fig. 6.
Compounds 1, 4 and 5 each contain one amidic
hydrogen atom and form dimmers via intermolecular –
P@Oꢀ ꢀ ꢀH–N– hydrogen bonds that in 1 is a centrosym-
metric dimmer (Table 6). In compound 2 (with four
independent molecules in the unit cell), the two con-
formers labeled with P(1), P(1A) [and also the two oth-
ers labeled with P(1B), P(1C)] are connected to each
other via two different –P@Oꢀ ꢀ ꢀH–N– hydrogen bonds
and form a noncentrosymmetric dimmer. The earlier
studied N-benzoyl, phosphoric triamides exist either in
the form of dimmeric aggregates [35] or as polymeric
chains [36].
3.2. X-ray crystallography investigation
Single crystals of compounds 1, 2, 4, 5 and 8 were ob-
tained from a solution of methanol and chloroform after
slow evaporation at room temperature. The crystal data
and the details of the X-ray analysis are given in Tables 2
and 3, selected bond lengths and angles in Tables 4
and 5. Molecular structures of these compounds are
shown in Figs. 2–6.
The two aliphatic rings of pyrrolidine groups in com-
pound 1 have puckered shape and they are not planar.
Compound 2 with six-membered ring amine group exists
as four symmetrically independent molecules in the
In molecules 1, 2, 4, 5 and 8 the phosphoryl and the
carbonyl groups are anti, Figs. 2–6. The phosphorus
atoms in these structures have slightly distorted tetrahe-
dral configuration. The bond angles around P(1) atoms
Table 3
Crystallographic data for 5 and 8
5
8
Empirical formula
Formula weight
T (K)
C
381.42
120(2)
0.71073 A
monoclinic
C2/c
19H29FN3O2P
C36H56Cl2F2N6O4P2Sn
926.40
120(2)
0.71073 A
˚
˚
k
Crystal system
Space group
Unit cell dimensions
monoclinic
P21/c
˚
a (A)
23.030(4)
9.2745(13)
20.585(3)
90
116.684(4)
90
3928.6(11)
8
1.290
0.167
1632
0.23 · 0.21 · 0.18
1.98–29.00
14.906(3)
8.6132(17)
16.538(3)
90
101.483(4)
90
2080.8(7)
2
1.479
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Dcalc (Mg mꢂ3
)
Absorption coefficient (mmꢂ1
F(000)
)
0.873
956
Crystal size (mm3)
0.45 · 0.3 · 0.15
1.39–28.00
ꢂ19 6 h 6 18, ꢂ11 6 k 6 9, ꢂ21 6 l 6 19
15430/4900 (0.0178)
(h = 28.00ꢁ) 97.5
h Range for data collection (ꢁ)
Limiting indices
Reflections collected/unique (Rint
Completeness to h (%)
ꢂ29 6 h 6 31, ꢂ12 6 k 6 12, ꢂ26 6 l 6 27
)
13691/5065 (0.0281)
(h = 29.00ꢁ) 97.0
Absorption correction
semi-empirical from equivalents
semi-empirical from equivalents
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
0.970 and 0.962
0.877 and 0.696
full-matrix least-squares on F2
5065/130/362
full-matrix least-squares on F2
4900/0/243
1.018
1.001
R1 = 0.0948, wR2 = 0.1608
R1 = 0.1676, wR2 = 0.1782
0.842 and ꢂ0.688
R1 = 0.0276, wR2 = 0.0549
R1 = 0.0357, wR2 = 0.0566
1.274 and ꢂ0.509
R indices (all data)
Largest difference in peak and hole (e A
ꢂ3
˚
)

K. Gholivand et al. / Polyhedron 25 (2006) 711–721
717
Table 4
˚
Selected bond lengths (A) and angles (ꢁ) for compounds 1, 2, 4 and 5
1
2
4
5
P(1)–O(1)
P(1)–N(1)
P(1)–N(2)
P(1)–N(3)
O(2)–C(1)
N(1)–C(1)
N(2)–C(8)
F(1)–C(5)
1.4863(10)
1.6899(11)
1.6239(12)
1.6390(12)
1.2207(16)
1.3763(15)
1.4841(16)
1.3615(16)
1.480(2)
1.683(3)
1.636(3)
1.625(3)
1.223(4)
1.378(4)
1.460(5)
1.366(4)
1.4801(17)
1.6839(16)
1.6246(18)
1.6318(18)
1.212(2)
1.375(3)
1.468(3)
1.358(2)
1.472(2)
1.675(3)
1.634(3)
1.626(4)
1.328(4)
1.365(4)
1.445(4)
1.321(4)
O(1)–P(1)–N(1)
O(1)–P(1)–N(2)
O(1)–P(1)–N(3)
N(2)–P(1)–N(1)
N(3)–P(1)–N(1)
N(2)–P(1)–N(3)
C(1)–N(1)–P(1)
104.66(5)
104.60(15)
118.86(16)
110.78(15)
105.13(16)
112.94(17)
104.64(16)
127.4(3)
104.63(9)
111.11(9)
118.30(11)
112.22(9)
106.52(9)
104.16(10)
127.28(14)
106.88(14)
109.89(19)
106.41(18)
116.41(19)
116.1(2)
110.37(6)
119.59(6)
115.73(6)
102.89(6)
103.93(6)
125.81(9)
100.7(3)
129.2(3)
Table 5
˚
Selected bond lengths (A) and angles (ꢁ) for compound 8
P(1)–O(1)
P(1)–N(1)
P(1)–N(2)
P(1)–N(3)
O(2)–C(1)
N(1)–C(1)
F(1)–C(5)
Sn(1)–C(18)
Sn(1)–O(1)
Sn(1)–Cl(1)
1.5012(14)
1.6921(17)
1.6260(17)
1.6201(17)
1.222(2)
1.384(3)
1.355(2)
2.1238(19)
2.2176(13)
2.5617(6)
C(18)–Sn(1)–C(18)#1
C(18)–Sn(1)–O(1)
C(18)–Sn(1)–O(1)#1
O(1)#1–Sn(1)–O(1)
C(18)–Sn(1)–Cl(1)
C(18)#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)
180.000(1)
87.51(7)
92.49(7)
180.0
90.25(6)
89.75(6)
91.91(4)
88.09(4)
180.0
145.42(9)
Symmetry code: #1: ꢂx, ꢂy + 2, ꢂz + 2.
Fig. 2. Molecular structure and atom-labeling scheme for P(O)(4-F-
C6H4C(O)NH)(NC4H8)2, compound 1 (50% probability ellipsoids).
in these compounds are in the range from 119.59(6)ꢁ in 1
to 100.7(3)ꢁ in 5, for the angles O(1)–P(1)–N(3) and
N(2)–P(1)–N(3), respectively, Tables 4 and 5. In these
compounds, the angles OPNamide (Namide is the nitrogen
atom of P(O)N(H)C(O) moiety) are lower than the an-
gles OPNamine (Namine is the nitrogen atom of P(O)NR
moiety). The P@O bond lengths in molecules 1, 2, 4, 5
and 8 are 1.4863(10), [1.480(2), 1.479(2), 1.471(2),
bond lengths in complex 8 is longer than those of ligand
2, but the C@O bond length in 8 is shorter than in 2,
Table 7. The C@O bond length in compound 5 with se-
ven-membered ring amine group has the longest,
˚
˚
1.328(4) A, and in compound 4, 1.212(2) A, has the
lowest value.
˚
1.475(3)], 1.4801(17), 1.472(2) and 1.5012(14) A that
˚
are larger than the normal P@O bond length (1.45 A)
The P–Namide bond lengths are longer than the
P–Namine bond lengths, because of the resonance interac-
tion of the Namide with the C@O p system that cause a par-
tial multiple bond character in C–Namide (the C–Namide
[37]. The P@O bond lengths in our previously reported
˚
structures are in the range from 1.4875(14) A in 12 to
˚
1.459(12) A in 10 (Table 7). The P@O and P–Namide

718
K. Gholivand et al. / Polyhedron 25 (2006) 711–721
Fig. 3. Molecular structure and atom-labeling scheme for P(O)(4-F-C6H4C(O)NH)(NC5H10)2, compound 2 showing four crystallographically
independent molecules in the lattice three of them have disordered forms (50% probability ellipsoids).
bond lengths are shorter than the C–Namine bond
lengths). All of these P–N bonds are shorter than the
typical P–N single bond length (1.77 A [37]). This is
the previously reported structures were in the range
from 1.6916(16) A (P–Namide in 12) to 1.590(15) A
(P–Namine in 10), respectively (Table 7).
˚
˚
˚
likely due to the electrostatic effects (polar bonds) which
overlap with P–N r bond [38]. The P–N bond lengths in
The environment of the nitrogen atoms is practically
planar. In compound 1 the angles C(11)–N(2)–C(8),

K. Gholivand et al. / Polyhedron 25 (2006) 711–721
719
Fig. 4. Molecular structure and atom-labeling scheme for P(O)(4-F-
C6H4C(O)NH)(NC4H8O)2, compound 4 (50% probability ellipsoids).
Fig. 6. Molecular structure and atom-labeling scheme for
Sn(CH3)2Cl2[P(O)(4-F-C6H4C(O)NH)(NC5H10)2]2, compound 8 (50%
probability ellipsoids).
C(11)–N(2)–P(1) and C(8)–N(2)–P(1) are 110.39(10)ꢁ,
126.80(9)ꢁ and 118.78(8)ꢁ, respectively, with average
118.7ꢁ. The sum of surrounding angles around N(1)
and N(3) atoms are 359.99ꢁ and 351.69ꢁ, respectively.
Similar results were obtained for the nitrogen atoms of
other structures 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.
In compound 8, the structure is symmetric and the
central Sn atom has octahedron coordination. The two
methyl groups (and also the two phosphoramidates
and the two chlorine atoms) are in trans positions and
the C(18)–Sn(1)–C(18)#1, O(1)–Sn(1)–O(1)#1 and
Cl(1)–Sn(1)–Cl(1)#1 bond angles are 180.0ꢁ and the
C–Sn–O, C–Sn–Cl and O–Sn–Cl bond angles are about
90ꢁ, Table 5. The Sn–C bond lengths (both are
˚
2.1238(19) A) are quite close to those reported in the lit-
˚
erature [39]. The Sn–Cl bond lengths are 2.5617(6) A ly-
˚
ing in the normal covalent radii 2.37–2.60 A [40]. The
˚
Sn–O bond lengths are 2.2176(13) A that are shorter
than sum of the van der Waals radii of Sn and O atoms
(3.70 A) [41].
Fig. 5. Molecular structure and atom-labeling scheme for P(O)(4-F-
C6H4C(O)NH)(NC6H12)2, compound 5 (50% probability ellipsoids).
˚
Table 6
˚
Hydrogen bonds D–Hꢀ ꢀ ꢀA for compounds 1, 2, 4, 5, and 8 (A and ꢁ)
Compound
D–Hꢀ ꢀ ꢀA
d(D–H)
d(Hꢀ ꢀ ꢀA)
d(Dꢀ ꢀ ꢀA)
\DHA
1
2
N1–H1Nꢀ ꢀ ꢀO1 [ꢂx + 1, ꢂy + 1, ꢂz]
0.845
0.86
0.91
0.75
0.85
2.001
1.96
1.99
2.17
2.07
2.842(2)
2.818(4)
2.886(4)
2.912(4)
2.916(4)
173.85
172
170
170
171
N1–H1Nꢀ ꢀ ꢀO1A
N1A–H1NAꢀ ꢀ ꢀO1
N1C–H1Cꢀ ꢀ ꢀO1B
N1B–H1Bꢀ ꢀ ꢀO1C
4
5
8
N1–H1Aꢀ ꢀ ꢀO1 [ꢂx, y, ꢂz + 1/2]
N1–H1Nꢀ ꢀ ꢀO1 [ꢂx, ꢂy + 1, ꢂz + 1]
N1–H1Nꢀ ꢀ ꢀCl1 [ꢂx, ꢂy + 2, ꢂz + 2]
0.86
0.82
0.90
2.06
2.02
2.50
2.904(3)
2.820(4)
3.320(2)
166
165
152

Table 7
P@O, P–Namide, P–Namine and C@O bond lengths (A) in compounds with five-, six- and seven-membered ring amine groups
˚
No. Compound
P@O
P–Namide
P–Namine
C@O
1
4-F-C6H4CðOÞNðHÞPðOÞR1
1.4863(10)
1.6899(11)
1.6239(12), 1.6390(12)
1.2207(16)
2
2
2
4-F-C6H4CðOÞNðHÞPðOÞR2
1.480(2), 1.479(2), 1.471(2), 1.475(3)
1.683(3), 1.681(3),
1.670(3), 1. 678(4)
1.625(3), 1.618(3) [conformer 1]
1.625(3), 1.633(3) [conformer 2]
1.636(3), 1.632(3) [conformer 3]
1.633(3), 1.626(3) [conformer 4]
1.223(4), 1.222(4), 1.222(4),
1.229(9), 1.238(10)
4
5
4-F-C6H4CðOÞNðHÞPðOÞR3
1.4801(17)
1.472(2)
1.6839(16)
1.675(3)
1.6246(18), 1.6318(18)
1.626(4), 1.634(3), 1.635(4), 1.641(4) 1.328(4), 1.312(4)
[disordered form]
1.212(2)
4-F-C6H4CðOÞNðHÞPðOÞR42
2
8
SnðCH3Þ2Cl2½4-F-C6H4CðOÞNðHÞPðOÞR22ꢃ2
1.5012(14)
1.6921(17)
1.6260(17), 1.6201(17)
1.222(2)
9a
C6H5CðOÞNðHÞPðOÞR1
1.487(3), 1.485(3)
1.679(4), 1.687(4)
1.618(4), 1.625(4) [conformer 1]
1.615(4), 1.618(3) [conformer 2]
1.217(5), 1.207(4)
2
10b
C6H5CðOÞNðHÞPðOÞR2
1.465(12), 1.459(12), 1.461(13), 1.464(13) 1.672(13), 1.690(13), 1.614(13), 1.605(15) [conformer 1]
1.235(17), 1.229(17), 1.230(17),
1.236(18)
2
1.691(14), 1.656(13)
1.615(17), 1.590(15) [conformer 2]
1.644(14), 1.631(14) [conformer 3]
1.623(13), 1.647(14) [conformer 4]
12c
C6H5CðOÞNðHÞPðOÞR4
1.4875(14)
R1
1.6916(16)
1.6369(16), 1.6345(15)
1.227(2)
2
R2
R3
R4
N
:
N
N
O
N
a
b
c
The data of this compound are given in [23].
The data of these compounds are given in [25].
The data of this compound are given in [42].

K. Gholivand et al. / Polyhedron 25 (2006) 711–721
[17] S.E. Denmark, J. Fu, J. Am. Chem. Soc. 125 (2003) 2208.
721
Appendix A. Supplementary data
[18] M.C. Cassani, M.J. Davis, P.B. Hitchcock, M.F. Lappert, Inorg.
Chim. Acta 358 (2005) 1595.
Spectroscopic data of compounds 1–8 can be ob-
tained as supplementary materials. Crystallographic
data for the structures in this paper have been deposited
with Cambridge Crystallographic Data Center as
supplementary publication nos. CCDC 259182
(C15H21F1N3O2P1), CCDC 259186 (C17H25F1N3O2P1),
CCDC 259185 (C15H21F1N3O4P1), CCDC 259184
(C19H29F1N3O2P1) and CCDC 259187 (C36H56Cl2-
F2N6O4P2Sn1). Copies of the data may be obtained on
application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (fax: +44 1223 336033; e-mail: deposit
@ccdc.cam.ac.uk or www: http://www.ccdc.cam.
ac.uk). Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.poly.2005.07.035.
´
´
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