Synthesis, spectroscopic characterization and crystal structure of a new acetyl phosphorylamidate P(O)[NHC(O)C6H4(4-NO 2)][N(CH(CH3)2)(CH2C 6H5)]2

Article abstract of DOI:10.1007/s10870-009-9582-4

A new acetyl phosphorylamidate P(O)[NHC(O)C₆H ₄(4-NO₂)][N(CH(CH₃)₂)(CH ₂C₆H₅)]₂ has been synthesized and characterized by elemental analysis, ¹H,

Full text of DOI:10.1007/s10870-009-9582-4

J Chem Crystallogr (2009) 39:874–880
DOI 10.1007/s10870-009-9582-4
ORIGINAL PAPER
Synthesis, Spectroscopic Characterization and Crystal Structure
of a New Acetyl phosphorylamidate P(O)[NHC(O)
C6H4(4-NO2)][N(CH(CH3)2)(CH2C6H5)]2
Mehrdad Pourayoubi Æ Fahimeh Sabbaghi
Received: 10 August 2008 / Accepted: 7 June 2009 / Published online: 21 June 2009
Ó Springer Science+Business Media, LLC 2009
Abstract A new acetyl phosphorylamidate P(O)[NH-
C(O)C6H4(4-NO2)][N(CH(CH3)2)(CH2C6H5)]2 has been
synthesisandcrystalstructuresofN-benzyl-2-propanaminium
O-methyl trichloroacetamidophosphate, [NH2(CH(CH3)2)
(CH2C6H5)][P(O)(NHC(O)CCl3)O(OCH3)] and N-benzyl-
propan-2-aminium (benzylisopropylamido)(2,2,2,-trifluo-
roacetamido) phosphate [NH2(CH(CH3)2)(CH2C6H5)][P(O)
(NHC(O)CF3)O(N(CH(CH3)2)(CH2C6H5))] have been
reported [5, 6]. In this paper, we report on the synthesis of a
new acetyl phosphorylamidate P(O)[NHC(O)C6H4(4-NO2)]
[N(CH(CH3)2)(CH2C6H5)]2 (Fig. 1) from the reaction
between 4-NO2–C6H4C(O)NHP(O)Cl2 and NH(CH(CH3)2)
(CH2C6H5). Characterization was done by elemental anal-
1
synthesized and characterized by elemental analysis, H,
13C and 31P NMR, IR and single crystal X-ray diffraction.
Single crystal X-ray analysis shows that it belongs to tri-
ꢀ
˚
clinic system, space group P1, with a = 10.5868(16) A,
˚
˚
b = 11.8058(18) A, c = 12.4364(19) A, a = 65.410(3)°,
3
˚
b = 67.492(4)°, c = 85.879(3)°, V = 1,298.6(3) A , and
Z = 2. The intermolecular POÁÁÁHN hydrogen bond makes
H-bonded dimer of molecule with Ci symmetry. In the
crystal network, the dimers are aggregated in the chain
arrays through p-stacking between p-NO2–C6H4–C(O)–
NH– moieties. Moreover, weak C–HÁÁÁO and C–HÁÁÁp
interactions exist in the crystal network.
1
ysis, H, 13C and 31P NMR, IR and single crystal X-ray
diffraction.
Keywords Synthesis Á Phosphorylamidate Á Crystal
structure Á NMR Á Centrosymmetic dimer Á N–HÁÁÁO
C–HÁÁÁO and C–HÁÁÁp interactions Á p–p stacking
Experimental
Instruments and Materials
All chemicals were purchased commercially and used
1
Introduction
without further purification. H, 13C and 31P NMR spectra
were determined on a Bruker Avance DRS 500 spec-
trometer. 1H and 13C chemical shifts were determined
relative to internal TMS, 31P chemical shift relative to 85%
H3PO4 as external standard. Infrared (IR) spectrum was
recorded on a Shimadzu model IR-60 spectrometer. Ele-
mental analysis was performed using a Heraeus CHN-O-
RAPID apparatus.
Acetyl phosphorylamidates, containing C(O)N(H)P(O)moiety
have attracted special interest because of bearing a close
structural resemblance to the b-diketone frame and acting as
effective chelating ligands [1], having biological properties
[2, 3] and urea inhibition [4]. In the previous work, the
M. Pourayoubi Á F. Sabbaghi
Preparation of the Title Compound
Department of Chemistry, Islamic Azad University-Zanjan
Branch, P.O. Box 49195-467, Zanjan, Iran
The reaction of phosphorus pentachloride (4.165 g,
20 mmol) and 4-nitrobenzamide (3.323 g, 20 mmol) in dry
CCl4 (70 mL) at 80 °C (3 h) and then the treatment of
formic acid (0.921 g, 20 mmol) at room temperature leads
M. Pourayoubi (&)
Department of Chemistry, Ferdowsi University of Mashhad,
91779 Mashhad, Iran
e-mail: mehrdad_pourayoubi@yahoo.com
123

J Chem Crystallogr (2009) 39:874–880
875
Table 1 Crystal data and structure refinement for P(O)[NHC(O)C6H4
(4-NO2)][N(CH(CH3)2)(CH2C6H5)]2
Empirical formula
Molecular weight
CCDC deposit no.
Temperature (K)
C27H33N4O4P
508.54
696934
120 (2)
H2C
CH2
CH3
˚
Wavelength (A)
0.71073
Triclinic
Crystal system
Space group
H3C
N
CH
N
ꢀ
P1
HC
˚
a (A)
10.5868 (16)
11.8058 (18)
12.4364 (19)
65.410 (3)
67.492 (4)
85.879 (3)
1,298.6 (3)
2
P
CH3
˚
b (A)
HN
H3C
O
˚
c (A)
a (°)
b (°)
c (°)
O
3
˚
V (A )
Z
Dx (g cm-3
)
1.301
l (Mo Ka) (mm-1
)
0.146
NO2
F(000)
540
Fig. 1 Chemical formula of title compound
Crystal size (mm3)
h range (°)
Limiting indices
0.4 9 0.24 9 0.2
1.91–27.00
to 4-NO2–C6H4C(O)NHP(O)Cl2. The solid (4-NO2–
C6H4C(O)NHP(O)Cl2) was washed with dry CCl4. To a
solution of (0.708 g, 2.5 mmol) 4-NO2–C6H4C(O)NH-
P(O)Cl2 in CCl4 (40 mL), a solution of N-isopropylben-
zylamine (1.492 g, 10 mmol) in CCl4 (10 mL) was added
dropwise at 0 °C. After 24 h, the solvent was removed in
vacuum and the solid was washed with distilled water. The
residue recrystallized in CH3CN–CH3OH. Anal. Calc. for
C27H33N4O4P: C, 63.77; H, 6.54; N, 11.02. Found: C,
63.85; H, 6.51; N, 11.06%. 31P NMR ([D6]DMSO): d
14.29. 13C NMR ([D6]DMSO): d 21.46 (d, 3J(P,C) =
2.7 Hz, 2 C, CH3), 21.90 (d, 3J(P,C) = 2.8 Hz, 2 C, CH3),
-13 B h B 13, -15 B k B 15,
-15 B l B 15
Reflections collected/unique
Completeness to h = 27.008
Absorption correction
12,532/5,667 [R(int) = 0.0305]
100.0%
Semi-empirical from
equivalents
Max. and min. transmission
Refinement method
GOF on F2
0.975 and 0.961
Full-matrix least-squares on F2
1.004
Final R indices [I [ 2r(I)]
R indices (all data)
Largest diff. peak and hole (e A-3) 0.346 and -0.317
R1 = 0.0589, wR2 = 0.1149
R1 = 0.0846, wR2 = 0.1281
˚
45.53 (d, 2J(P,C) = 5.1 Hz,
2 C, CH), 47.64 (d,
2J(P,C) = 5.0 Hz, 2 C, CH2), 123.26 (s), 126.54 (s),
127.66 (s), 127.90 (s), 129.37 (s), 139.69 (d,
3J(P,C) = 8.9 Hz), 141.11 (d, J(P,C) = 2.4 Hz), 149.30
3
determination are presented in Table 1. Data were col-
lected at 120 K on a Bruker SMART 1000 CCD [7] single
crystal diffractometer with graphite monochromated Mo
(s), 167.04 (s, 1 C, C=O). 1H NMR ([D6]DMSO): d 0.98 (d,
3J(H,H) = 6.4 Hz, 6 H, 2 CH3), 0.99 (d, 3J(H,H) =
6.5 Hz, 6 H, 2 CH3), 3.89 (m, 2 H, 2 CH), 4.31 (m, 4 H, 2
CH2), 7.17–7.96 (m, 10 H, Ar–H), 8.21 (d, 3J(H,H) =
˚
Ka radiation (k = 0.71073 A) in the range of 1.91°
\ h \ 27.00°. The structure was refined with SHELXL-97
[8] by full matrix least squares on F2. The hydrogen atom
of NH group was found in difference Fourier synthesis.
The H(C) atom positions were calculated. All hydrogen
atoms were refined in isotropic approximation in riding
model with the Uiso(H) parameters equal to 1.2 Ueq(Ci), for
methyl groups equal to 1.5 Ueq(Cii), where U(Ci) and
U(Cii) are respectively the equivalent thermal parameters
of the carbon atoms to which corresponding H atoms are
bonded. A semi-empirical absorption correction was per-
formed using the SADABS program [9].
3
7.0 Hz, 2 H, Ar–H), 8.26 (d, J(H,H) = 7.0 Hz, 2 H, Ar–
H), 9.65 (b, 1 H, NH). IR (KBr, cm-1): 3,050, 2,971, 2,701,
1,661 (mC=O), 1,601, 1,520, 1,456, 1,346, 1,275, 1,217,
1,064, 944, 849, 787, 712.
Crystal Structure Determination and Refinement
A
colorless prismatic crystal (0.4 mm 9 0.24 mm
9 0.2 mm) was selected for X-ray crystallography exper-
iment. Crystal data and refinement details for the structure
123

876
J Chem Crystallogr (2009) 39:874–880
˚
Results and Discussion
Description of the Crystal Structure
Table 3 Selected bond lengths (A) and angles (°) for P(O)[NH-
C(O)C6H4(4-NO2)][N(CH(CH3)2)(CH2C6H5)]2
P(1)–O(1)
1.4801(17)
1.636(2)
O(4)–N(2)
1.223(3)
1.370(3)
1.486(3)
1.485(3)
1.488(3)
1.466(3)
116.2(2)
121.79(17)
120.08(17)
117.67(19)
119.18(16)
122.15(16)
123.1(2)
119.0(2)
117.9(2)
P(1)–N(3)
N(1)–C(1)
Single crystals of title compound were obtained from a
solution of CH3CN–CH3OH after slow evaporation at room
temperature. The final atomic coordinates and equivalent
isotropic displacement parameters and selected geometric
parameters are given in Tables 2 and 3. The phosphoryl
P(1)–N(4)
1.644(2)
N(2)–C(5)
P(1)–N(1)
1.694(2)
N(3)–C(11)
O(2)–C(1)
1.216(3)
N(3)–C(8)
O(3)–N(2)
1.219(3)
N(4)–C(21)
O(1)–P(1)–N(3)
O(1)–P(1)–N(4)
N(3)–P(1)–N(4)
O(1)–P(1)–N(1)
N(3)–P(1)–N(1)
N(4)–P(1)–N(1)
C(1)–N(1)–P(1)
O(3)–N(2)–O(4)
O(3)–N(2)–C(5)
118.24(10)
108.78(10)
107.25(10)
105.31(10)
104.71(11)
112.63(10)
126.67(17)
124.1(2)
C(11)–N(3)–C(8)
C(11)–N(3)–P(1)
C(8)–N(3)–P(1)
C(21)–N(4)–C(18)
C(21)–N(4)–P(1)
C(18)–N(4)–P(1)
O(2)–C(1)–N(1)
O(2)–C(1)–C(2)
N(1)–C(1)–C(2)
Table 2 Atomic coordinates (9104) and equivalent isotropic dis-
2
placement parameters (A 9 10 ) for P(O)[NHC(O)C6H4(4-NO2)]
3
˚
[N(CH(CH3)2)(CH2C6H5)]2
x
y
z
Ueqa
P(1)
8,354(1)
9,287(2)
7,182(2)
9,917(2)
8,441(2)
8,561(2)
9,046(2)
8,646(2)
6,773(2)
7,942(2)
8,248(2)
9,044(3)
9,289(3)
8,718(2)
7,901(3)
7,674(3)
8,143(3)
7,481(3)
9,220(3)
9,703(3)
8,299(1)
9,014(2)
7,794(2)
1,253(1)
1,435(2)
-427(2)
29(1)
31(1)
42(1)
50(1)
53(1)
29(1)
39(1)
32(1)
30(1)
30(1)
29(1)
36(1)
38(1)
33(1)
34(1)
34(1)
39(1)
53(1)
52(1)
36(1)
36(1)
38(1)
46(1)
49(1)
49(1)
42(1)
38(1)
52(1)
51(1)
34(1)
31(1)
35(1)
42(1)
45(1)
42(1)
36(1)
O(1)
O(2)
O(3)
O(4)
N(1)
N(2)
N(3)
N(4)
C(1)
117.9(2)
12,642(2)
11,389(2)
9,088(2)
11,744(2)
6,865(2)
8,239(2)
8,754(2)
9,621(2)
10,766(2)
11,480(3)
11,021(2)
9,909(2)
9,203(2)
5,815(2)
4,697(3)
5,451(3)
6,595(3)
6,650(2)
7,790(3)
7,845(3)
6,754(3)
5,636(3)
5,579(3)
7,620(3)
8,581(3)
6,756(3)
9,012(2)
8,284(2)
7,515(2)
6,816(3)
6,895(3)
7,687(3)
8,367(3)
-6,854(2)
-6,748(2)
-304(2)
-6,262(2)
1,431(2)
2,254(2)
-931(2)
-2,328(2)
-2,988(2)
-4,280(2)
-4,866(2)
-4,228(2)
-2,945(2)
2,737(2)
2,745(3)
3,323(3)
393(2)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
a
11,172(3)
11,892(3)
13,225(3)
13,877(3)
13,183(3)
11,843(3)
5,582(3)
4,784(3)
4,620(3)
6,486(3)
6,234(2)
7,176(3)
6,932(3)
5,734(3)
4,804(3)
5,047(3)
291(2)
-109(2)
-197(3)
100(3)
449(3)
545(3)
2,282(2)
1,606(3)
3,645(3)
2,970(2)
4,378(2)
4,743(2)
6,031(3)
6,963(2)
6,613(2)
5,329(2)
Fig. 2 Molecular structure of P(O)[NHC(O)C6H4(4-NO2)][N(CH
(CH3)2)(CH2C6H5)]2 in representation of atoms via thermal ellipsoids
at 50% probability level (all hydrogen atoms except H(1N) are
omitted for clarity)
and the carbonyl groups are anti and the phosphorus atom
has a slightly distorted tetrahedral configuration (Fig. 2).
The bond angles around the P atom are in the range of
104.71(11)°–118.24(10)°. P(1)–N(3) and P(1)–N(4) bond
Ueq is defined as one-third of the trace of the orthogonalized Uij
tensor
˚
˚
lengths (1.636(2) A and 1.644(2) A) are significantly
123

J Chem Crystallogr (2009) 39:874–880
877
˚
shorter than the typical P–N single bond length (1.77 A)
[10]. The shortening of P–N bond lengths is likely related
to an electrostatic effect (polar bond) which overlaps with
Table 4 Hydrogen bonds
NO2)][N(CH(CH3)2)(CH2C6H5)]2
for
P(O)[NHC(O)C6H4(4-
D–HÁÁÁA d(D–H) d(HÁÁÁA) d(DÁÁÁA) \(DHA)
N(1)–H(1N)ÁÁÁO(1)#1 0.91(4) 1.91(4) 2.801(3) 168(3)
Symmetry transformations used to generate equivalent atoms: #1
˚
P–N r bond [11]. The P(1)–N(1) bond length (1.694(2) A)
is longer than the P(1)–N(3) and P(1)–N(4) bond lengths
due to the resonance interaction of N(1) nitrogen atom lone
pair with the C=O system (and less interaction with P=O)
that causes a partial multiple bond character in N(1)–C(1)
(compare N(1)–C(1) with other N–C bond lengths
(Table 3). The environment of the nitrogen atoms is
practically planar. In the title compound, the angles C(11)–
N(3)–C(8), C(11)–N(3)–P(1) and C(8)–N(3)–P(1) are
116.2(2)°, 121.79(17)° and 120.08(17)°, respectively (with
average 119.4°). A similar result was obtained for the bond
angles around N(4) atom (average = 119.7°). Furthermore,
the angle C(1)–N(1)–P(1) is 126.67(17)°. These results
confirm the sp2 hybridization for the nitrogen atoms,
although due to repulsion and steric interactions and elec-
tronic effect, some angles are greater and the others are
-x ? 2, -y ? 2, -z
orientation of these moieties in crystal packing, Fig. 4).
The planes of p-NO2–C6H4–C(O)–NH– moieties of
neighboring molecules are parallel (0.0(1)°) and are
˚
situated at 3.36(2) A from each other; compare it with the
distance between the planes of p-H3C–C6H4–NH moieties
˚
(3.26(1) A [20]) in [(CH3)2N][p-H3C–C6H4–O]P(O)
[p-H3C–C6H4–NH]). The p-stacking between p-NO2–C6H4–
C(O)–NH– moieties is off-center stacking, the distance
between the centers of the interacting phenyl rings is
˚
4.046(4) A. The concept of H bonds has been extended to
C–HÁÁÁY bonding (where Y is an electronegative atom or
˚
the p system [21, 22]). Previous studies have suggested that
smaller than 120°. The P=O bond length, 1.4801(17) A, is
˚
˚
longer than the normal P=O bond length (1.45 A) [10]. The
C–HÁÁÁO hydrogen bonds occur in the range of 3.0–4.0 A
for CÁÁÁO distances and more than 110° for the bond angles
[23, 24]. Figure 5 indicates a view of normal N(1)–
H(1N)ÁÁÁO(1) and weak C(3)–H(3A)ÁÁÁO(1) and C(15)–
H(15A)ÁÁÁO(2) hydrogen bonds. The weak C–HÁÁÁO
hydrogen bonds in the title compound [C(3)ÁÁÁO(1) =
amidic hydrogen atom of title compound is involved in
intermolecular –P=OÁÁÁH–N– hydrogen bond (Fig. 3;
Table 4) to form a dimer with Ci symmetry (centrosym-
metric dimer). The donorÁÁÁacceptor distances for the
–P=OÁÁÁH–N hydrogen bond in the title compound is in the
range of the values which have been observed for the other
phosphoramidate compounds, Table 5. H-bonded dimers in
the crystal structure form chains through p-stacking
between p-NO2–C6H4–C(O)–NH– moieties (see the
˚
3.165(3) A, \C–H–O = 155.6° and C(15)ÁÁÁO(2) =
˚
3.517(3) A, \C–H–O = 157.7°] are in the range of the
previous results for the phosphoryl compounds, for exam-
ple in P(O)(OCH3)2(NHC6H4(4-NO2): C(sp2)ÁÁÁO(phos-
3
˚
˚
phoryl) = 3.352 A and C(sp )ÁÁÁO(nitro) = 3.302 A [25]
and in P(O)[4-CH3–C5H9N]2[NHC6H4(4-NO2)]: C(sp2)ÁÁÁO
(phosphoryl) = 3.288 A, C(sp3)ÁÁÁO(nitro) = 3.429 and
˚
˚
3.435 A [13]. A view of C(7)–H(7A)ÁÁÁp and C(25)–
H(25A)ÁÁÁp interactions is given in Fig. 6 [r(C(7)ÁÁÁmean-
˚
˚
plane) = 3.562(3) A, r(H(7A)–C(25)) = 2.854 A, \C–H–
˚
C = 137.2° and r(C(25)ÁÁÁmeanplane) = 3.467(4) A, r(H(25)–
˚
C(15)) = 2.884 A, \C–H–C = 131.7°]. The C–H bond
points away from the ring although the hydrogen is close to
a carbon (type VI C–HÁÁÁp interaction according to the
classification of Malone et al. [26]). The distances of
interacting H atoms to phenyl ring centroid (3.44 and
˚
3.53 A) in P(O)[NHC(O)C6H4(4-NO2)][N(CH(CH3)2)(CH2
C6H5)]2 are more than the values for [P(O)(O)(NHC(O)
CF3)(N(CH(CH3)2)(CH2C6H5))][NH2(CH(CH3)2)(CH2C6H5)]
˚
(3.26 A [6]) and [(CH3)2N]P(O)[NH(iso-C3H7)][p-OC6H4
˚
–CH3] (3.31 A) [19].
Spectroscopic Characterization
As can be seen in X-ray structure of the title compound, the
P=OÁÁÁH–Namide hydrogen bond leads to a dimeric aggre-
gate in the solid state, which means the phosphoryl oxygen
Fig. 3 The fragment of crystal packing of P(O)[NHC(O)C6H4(4-
NO2)][N(CH(CH3)2)(CH2C6H5)]2 along the crystallographic plane ab
(all hydrogen atoms except H(1N) are omitted for clarity)
123

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J Chem Crystallogr (2009) 39:874–880
Table 5 DonorÁÁÁacceptor (NÁÁÁO) distances for N–HÁÁÁO=P hydrogen bonds in some phosphoramidate compounds
˚
No.
Compound
DÁÁÁA (A)
Ref.
1
P(O)(C6H5C(O)NH)[N(CH3)(CH2C6H5)]2
P(O)(CCl3C(O)NH)[N(CH3)(CH2C6H5)]2
P(O)(CF3C(O)NH)[N(CH3)(CH2C6H5)]2
P(O)(4-NO2–C6H4NH)[4-CH3–NC5H9]2
2.809(3)
[12]
[12]
[13]
[13]
[14]
[14]
[14]
[14]
[15]
[16]
[16]
[16]
[17]
[17]
[18]
[5]
2
2.794(2)
3
2.747(4)
4
2.770(2)
5
P(O)(4-F–C6H4C(O)NH)[NC4H8]2
a
P(O)(4-F–C6H4C(O)NH)[NC5H10 2
2.842(2)
6
]
2.818(4), 2.886(4), 2.912(4), 2.916(4)
2.904(3)
7
P(O)(4-F–C6H4C(O)NH)(NC4H8O)2
8
P(O)(4-F–C6H4C(O)NH)(NC6H12)2
P(O)(C6H5C(O)NH)(NC4H8)2b
2.820(4)
9
2.855(6), 2.886(5)
2.774(2)
10
11
12
13
14
15
16
17
a
P(O)(4-F–C6H4C(O)NH)[NH–C(CH3)3]2
P(O)(4-F–C6H4C(O)NH)[NH–CH2C6H5]2c
P(O)(4-F–C6H4C(O)NH)[N(CH3)(CH2C6H5)]2
P(O)(C6H5C(O)NH)(NC3H6)2b
2.834(2), 3.015(2), 2.937(2)
2.8055(14)
2.817(1), 2.815(1)
2.816(3)
P(O)(C6H5C(O)NH)(NC6H12)2
P(O)[(C6H5)(CH3)CH–NH](p-OC6H4CH3)2b
2.839(6), 2.817(6)
2.811(2), 2.727(2), 2.743(2)
2.849(4)
[NH2(CH(CH3)2)(CH2C6H5)][P(O)(NHC(O)CCl3)O(OCH3)]
P(O)[NHCH(CH3)2][(CH3)2N][p-H3C–C6H4–O]
[19]
Compound contains four independent molecules in crystal lattice
b
c
Two independent molecules
The first DÁÁÁA distance in the table is related to P=OÁÁÁH–Namide, two others are related to P=OÁÁÁH–Namine
Fig. 4 A view of H-bonded
dimers with Ci symmetry and
the chain array through
p-stacking between p-NO2–
C6H4–C(O)–NH– moieties
atom is the better H-acceptor than the carbonyl oxygen
atom. This finding is in agreement with the theoretical
studies on compounds with –P(OP)XC(OC)– system. The
theoretical investigation shows that the OP atom is a better
electron donor relative to the OC counterpart as a result of
the more partial negative charge (d-) on the OP atom rel-
ative to the OC [27]. In title compound, the m(C=O)
stretching frequency appears at 1,661 cm-1 wave number.
very sensitive to the formation of hydrogen bonding (red-
shift of the absorption band, band broadening or intensifi-
~
cation). For N–HÁÁÁO hydrogen bonds, the tN–H is
depending on the H-bond strength or donorÁÁÁacceptor
distance (NÁÁÁO). For title compound, the band at
3,050 cm-1 is assigned to N–Hamide. The wave number is
close to the ones which have been observed for ClF2CC
(O)NHP(O)Cl2 and CF3C(O)NHP(O)Cl2 (3,064 and
3,093 cm-1) [28, 29]. This relative low wave number for
~
The frequency of the N–H stretching vibration (tN–H) is
123

J Chem Crystallogr (2009) 39:874–880
879
Fig. 5 A view of normal
N–HÁÁÁO and weak C–HÁÁÁO
hydrogen bonds in the crystal
network
Fig. 6 A view of C–HÁÁÁp
interactions in the crystal
network
an N–H stretching vibrational mode can be explained by
the N–HÁÁÁO intermolecular interactions as reported on
related acetyl phosphorylamidate compounds [28]. The
NHamide is placed between two withdrawing groups (PO
and CO) which causes an increase in the acidity of the H
atom. Appearance of the NHamide signal at 9.65 ppm in 1H
NMR spectrum confirms this fact. Moreover, the phos-
phorus–hydrogen coupling constant, 2J(PNH) was not
observed. The P–C coupling constants give rise to two
doublet signals for two non-equivalent methyl carbon
atoms of isopropyl moieties at 21.46 ppm (3J(P,C) =
2.7 Hz) and 21.90 ppm (3J(P,C) = 2.8 Hz). Moreover, the
CH and CH2 carbon atoms show P–C coupling constants at
45.53 ppm (2J(P,C) = 5.1 Hz) and 47.64 ppm (2J(P,C) =
5.0 Hz), which means that for these aliphatic carbon atoms
2J(P,C) [ 3J(P,C). Also, the ipso C atoms of the phenyl
moieties show P–C coupling constants (3J(P,C) = 2.4 and
8.9 Hz). Phosphorus chemical shift in the title compound
was observed at 14.29 ppm in 31P NMR spectrum.
Supplementary Material
CCDC 696934 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
at www.ccdc.cam.ac.uk/conts/retrieving.html or from the
Cambridge Crystallographic Data Centre (CCDC), 12 Union
Road, Cambridge CB2 1BZ, UK, Fax: ?44-1223-336033,
e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgments Support of this investigation by Islamic Azad
University-Zanjan Branch is gratefully acknowledged.
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