The spectroscopy and structure of new 1,3,2-diazaphospholes and 1,3,2-diazaphosphorinanes

Article abstract of DOI:10.1080/10426507.2012.743547

New 1,3,2-diazaphospholes and 1,3,2-diazaphosphorinanes with formula 2,4-Cl₂-C6H₃-C(O)NHP(O)X where X = (1), (2), (3), and (4) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy, and elemental analysis. The ³¹P NMR spectra revealed that the phosphorus atoms are more deshielded in the diazaphospholes than in the diazaphosphorinanes. The ¹³C NMR spectrum of 2 indicated that ²JPC(aliphatic) = 14.2 Hz for the endocyclic carbon atom is larger than that for the exocyclic CH₃ carbon atom (5.2 Hz). Furthermore, for diazaphosphorinanes, ³JPC(aliphatic) ≈ 2 × ²JPC(aliphatic). The molecular structure of compound 2 was determined by X-ray crystallography. In this structure, a centrosymmetric dimer is formed via connection of two molecules by strong intermolecular N-HcccO hydrogen bonds. The presence of weak intermolecular C-HcccO and C-HcccCl hydrogen bonds creates a three dimensional polymeric chain in the crystal lattice.

Full text of DOI:10.1080/10426507.2012.743547

This article was downloaded by: [Northeastern University]
On: 28 December 2014, At: 00:43
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
The Spectroscopy and Structure of
New 1,3,2-Diazaphospholes and 1,3,2-
Diazaphosphorinanes
N. Oroujzadeh a , K. Gholivand a & Z. Shariatinia b
a Department of Chemistry , Tarbiat Modares University , Tehran ,
Iran
b Department of Chemistry , Amirkabir University of Technology ,
Tehran , Iran
Accepted author version posted online: 10 Dec 2012.Published
online: 08 May 2013.
To cite this article: N. Oroujzadeh , K. Gholivand & Z. Shariatinia (2013) The Spectroscopy and
Structure of New 1,3,2-Diazaphospholes and 1,3,2-Diazaphosphorinanes, Phosphorus, Sulfur, and
Silicon and the Related Elements, 188:1-3, 183-191, DOI: 10.1080/10426507.2012.743547
To link to this article: http://dx.doi.org/10.1080/10426507.2012.743547
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Phosphorus, Sulfur, and Silicon, 188:183–191, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.743547
THE SPECTROSCOPY AND STRUCTURE
OF NEW 1,3,2-DIAZAPHOSPHOLES
AND 1,3,2-DIAZAPHOSPHORINANES
N. Oroujzadeh,1 K. Gholivand,1 and Z. Shariatinia2
1Department of Chemistry, Tarbiat Modares University, Tehran, Iran
2Department of Chemistry, Amirkabir University of Technology, Tehran, Iran
GRAPHICAL ABSTRACT
Abstract New 1,3,2-diazaphospholes and 1,3,2-diazaphosphorinanes with formula 2,4-Cl2-
C6H3-C(O)NHP(O)X where X =
(1),
(2),
(3),
NH(CH2)2NH
NH(CH2)3NH
CH3N(CH2)2NCH3
NHCH C(CH ) CH NH
and
(4) were synthesized and characterized by 1H, 13C, 31P NMR, IR
2
3
2
2
spectroscopy, and elemental analysis. The 31P NMR spectra revealed that the phosphorus atoms
are more deshielded in the diazaphospholes than in the diazaphosphorinanes. The 13C NMR
spectrum of 2 indicated that 2JPC(aliphatic) = 14.2 Hz for the endocyclic carbon atom is larger
than that for the exocyclic CH3 carbon atom (5.2 Hz). Furthermore, for diazaphosphorinanes,
2
3JPC(aliphatic) ≈ 2 × JPC(aliphatic). The molecular structure of compound 2 was determined by
X-ray crystallography. In this structure, a centrosymmetric dimer is formed via connection
. . .
of two molecules by strong intermolecular N–H O hydrogen bonds. The presence of weak
. . .
. . .
intermolecular C–H O and C–H Cl hydrogen bonds creates a three dimensional polymeric
chain in the crystal lattice.
Received 13 September 2012; accepted 22 October 2012.
The financial support of this work by the Research Council of Tarbiat Modares University is gratefully
acknowledged.
Address correspondence to K. Gholivand, Department of Chemistry, Tarbiat Modares University, P.O. Box
14115-175, Tehran, Iran. E-mail: gholi kh@modares.ac.ir
183

184
K. GHOLIVAND ET AL.
Keywords 1,3,2-Diazaphosphole; 1,3,2-diazaphosphorinane; NMR; X-ray crystallography;
hydrogen bonds
INTRODUCTION
Recently, there has been great interest in the chemistry of heterocyclic diazaphos-
phorinanes and diazaphospholes due to their significant pharmacological properties.1,2
Cyclophosphamide and ifosphamide are well-known diazaphosphorinanes that exhibit an-
ticancer activities.3–6 The synthesis and structural properties of some diazaphospholes was
reported by Spilling et al.7 Diazaphosphole derivatives have been used in organic8 and
asymmetric9 synthesis as well as in coordination chemistry.10 The preparation and crystal
structures of several tungsten complexes bearing diazaphospholes has been investigated.11
In this area, conformational studies, X-ray structure determinations, and complexation of
semirigid macrocyclic phosphonamides have also been reported.12 The two polymorphs of
a diazaphosphole oxide were determined by Norman et al.13 Furthermore, the synthesis and
structure of mono- and diphosphorus containing diazaphospholes were reported.14
In this work, following on our previous results about diazaphospholes and diaza-
phosphorinanes,15–19 new derivatives of this family were synthesized and characterized by
multinuclear (1H, 13C and 31P) NMR, IR spectroscopy, and elemental analysis. Also, the
molecular structure of compound 2 was determined by single crystal X-ray diffraction. The
effects of the substituents on the spectroscopic results were interpreted and are discussed.
RESULTS AND DISCUSSION
Spectroscopic Study
In this study, new phosphoramides 1–4 were synthesized from the reaction of
POCl3/RPOCl2 with different amines (Scheme 1) and fully characterized by NMR and
IR spectroscopy. A summary of the spectroscopic data of these compounds is given in
1
Table 1. The 31P{ H} NMR spectra indicate a phosphorus chemical shift, δ31P, in the range
of 21.0 ppm (in 1) to 1.1 ppm (in 4) displaying very different electron donation power of
the substituents at the phosphorus atoms. A comparison of the δ31P values indicates that
the shielding of the phosphorus atom changes in the order 1 < 2 < 3 < 4. Moreover, the
phosphorus atoms in the diazaphospholes 1 and 2 are more deshielded than in the diaza-
phosphorinanes 3 and 4. Comparing the δ31P values of compounds 1 and 2 and also those
of compounds 3 and 4 demonstrates that the derivatives containing endocylic N-methyl
groups have more shielded phosphorus atoms than those including endocyclic NH moi-
eties. This is due to the increased electron donation to the phosphorus atoms by methyl
groups.
The 1H NMR spectrum of 4 shows geminal 2JHH coupling constant of 11.9 Hz as well
as vicinal couplingconstant 3JPNCH =26.7Hz. Suchcouplings werealsoobservedinourpre-
viously reported similar phosphorus compounds.20–23 The 13C NMR spectra of compounds
2,3
2
1–4 display
J
coupling constants; the value of JPC(aliphatic) for the endocyclic
PC(aliphatic)
carbon atom of 2 (14.2 Hz) is larger that for the exocyclic CH3 carbon atom (5.2 Hz).
3
Furthermore, it becomes evident that for diazaphosphorinanes 3 and 4 JPC(aliphatic)
≈
2 × JPC(aliphatic). The values of 3JPC(aromatic) in these molecules are about 8.0 Hz.
2

SPECTROSCOPY AND STRUCTURE OF NEW 1,3,2-DIAZAPHOSPHOLES
185
Scheme 1
The analysis of the IR spectra indicates that the P=O and C=O bonds in the di-
azaphospholes 1 and 2 are stronger than those in the diazaphosphorinanes 3 and 4. Also,
the stretching frequencies ν(P–Namine) and ν(P–Namide) are observed at about 1011–1097
and 886–956 cm−1, respectively, indicating that the P–Namine bonds are stronger than the
P–Namide bonds. This matter has been confirmed by the results of X-ray crystallography of
compound 2 as well as our earlier investigated structures.21–23
X-Ray Crystallography
To gain more insight into the structural properties of the diazaphospholes, the structure
of compound 2 has been determined by single crystal X-ray diffraction. Single crystals of
the compound were obtained from a solution of CH3CN/n-hexane at room temperature.
The crystallographic data and the details of the X-ray analysis are presented in Table 2,
selected bond lengths and angles are given in Table 3. The ORTEP view of the molecular
structure and of the unit cell packing is shown in Figures 1 and 2, respectively.
Table 1 Selected spectroscopic NMR and IR data of compounds 1–4
δ31
2JPC(aliphatic)
(Hz)
3JPC(aliphatic) 3JPC(aromatic) ν(P O) ν(C O) ν(P–Namine
)
ν(P–Namide)
(cm−1
)
Compound P (ppm)
(Hz)
(Hz)
(cm−1
)
(cm−1
)
(cm−1
)
1
2
3
4
21.0
17.3
3.3
—
—
—
6.2
4.7
8.7
8.7
8.1
8.0
1202
1209
1165
1185
1678
1679
1671
1669
1045
1032
1011
1097
917
941
886
956
5.2 (CH3), 14.2 (CH2)
3.03
1.8
1.1

186
K. GHOLIVAND ET AL.
Table 2 Crystallographic data for compound 2
Chemical formula
Formula weight
Crystal system, space group
Temperature (K)
a, b, c (Å)
C11H14Cl2N3O2P
322.12
Triclinic, P-1
120(2)
7.5550(8), 9.9104(10), 10.0411(10)
109.777(1), 90.778(2), 94.626(2)
704.49(12)
α, β, γ (◦)
Volume (Å3)
Z
2
Density (calculated, g/cm3)
Absorption coefficient (mm−1
Crystal size (mm3)
1.519
0.575
)
0.24 × 0.18 × 0.14
Theta range for data collection (◦)
Index ranges
Reflections collected
2.16 to 28.00
−9 ≤ h ≤ 9, −13 ≤ k ≤ 13, −13 ≤ l ≤ 13
7280
Independent reflections
3385 [Rint = 0.0223]
Completeness to theta = 28.00◦
99.9%
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Semi-empirical from equivalents
0.927 and 0.873
Full-matrix least-squares on F2
3385/0/174
1.011
Final R indices for 3613 refl. with [I > 2sigma(I)]
R indices (all data)
Largest diff. peak and hole
R1 = 0.0437, wR2 = 0.1038
R1 = 0.0504, wR2 = 0.1085
0.539 and –0.518 e.Å−3
The five-membered aliphatic ring adopts a puckered shape. The P=O bond length
in the molecule is 1.483(2) Å, which is slightly longer than the normal P=O bond length
(1.45 Å).24 The phosphorus atom adopts a slightly distorted tetrahedral configuration; the
surrounding angles around the P atom are in the range of 95.40(9)◦–120.06(9)◦. All P–N
bonds (1.631(2), 1.640(2), and 1.689(2) Å) are shorter than the typical P–N single bonds
(1.77 Å)24 revealing partial multiple bond character. The P–Namide bond lengths are longer
than the P–Namine bond lengths because of the resonance interaction of the Namide with the
C=O π system, which causes a partial multiple bond character of the C–Namide bond (the
C–Namide bond lengths are shorter than the C–Namine bond lengths, that is, N(3)–C(5) =
1.374(3) Å while N(1)–C(1) = 1.469(3) Å, N(1)–C(3) = 1.451(3) Å). The O(2)–C(5) and
Table 3 Selected bond lengths (Å) and angles (◦) for compound 2
P(1)–O(1)
P(1)–N(1)
P(1)–N(2)
P(1)–N(3)
Cl(1)–C(7)
Cl(2)–C(9)
O(2)–C(5)
N(1)–C(3)
N(1)–C(1)
N(2)–C(4)
N(2)–C(2)
N(3)–C(5)
1.483(2)
1.631(2)
1.640(2)
1.689(2)
1.737(2)
1.741(2)
1.223(2)
1.451(3)
1.469(3)
1.454(3)
1.463(3)
1.374(3)
O(1)–P(1)–N(1)
O(1)–P(1)–N(2)
N(1)–P(1)–N(2)
O(1)–P(1)–N(3)
N(1)–P(1)–N(3)
N(2)–P(1)–N(3)
C(3)–N(1)–C(1)
C(3)–N(1)–P(1)
C(1)–N(1)–P(1)
C(4)–N(2)–C(2)
C(4)–N(2)–P(1)
C(2)–N(2)–P(1)
120.0(1)
115.3(1)
95.4(1)
103.7(1)
109.7(1)
113.0(1)
118.0(2)
124.6(2)
113.6(1)
118.6(2)
122.7(2)
112.9(1)

SPECTROSCOPY AND STRUCTURE OF NEW 1,3,2-DIAZAPHOSPHOLES
187
Figure 1 ORTEP view of the molecular structure of compound 2 in the crystal.
Cl(1)–C(7), Cl(2)–C(9) bond lengths are 1.223(2) Å and 1.737(2), 1.741(2) Å, respectively.
In the five-membered ring the endocyclic C–N bonds are longer than the exocyclic ones.
For example, N(2)–C(2) = 1.463(3) Å but N(2)–C(2) = 1.454(3) Å.
In compound 2, the angles P(1)–N(1)–C(1), P(1)–N(1)–C(3), and C(1)–N(1)–C(3)
are 113.6(1)◦, 124.6(2)◦, and 118.0(2)◦, respectively, with average of 118.71◦. The sum of
the angles around N(2) and N(3) are 354.20◦ and 359.72◦. The angles OPNamide (Namide
is the nitrogen atom of the P(O)N(H)C(O) moiety) are smaller than the angles OPNamine
(Namine is the nitrogen atom of P(O)NR moiety). This was also observed in our previously
reported compounds.21–23
In the structure of compound 2, a centrosymmetric dimer is formed through con-
nection of two molecules by strong intermolecular N(3)–H(3N)···O (1) hydrogen bonds
(D H = 0.95 Å, H···A = 1.90 Å, D···A = 2.844(2) Å, ∠D H···A = 177.0◦, symmetry
codes = −x + 1,−y + 2,−z + 1). Considering weak intermolecular C(8)–H(8A)···O(1),
Figure 2 The unit cell packing of compound 2.

188
K. GHOLIVAND ET AL.
Figure 3 The three-dimensional polymeric chain formed by strong and weak hydrogen bonds in compound 2
(Color figure available online).
C(1)–H(1B)···O(2), and C(3)–H(3B)···Cl(2) interactions a three dimensional polymeric
chain is produced in the crystalline network (Figure 3).
EXPERIMENTAL
X-Ray Measurements
X-ray data of compound 2 were collected with a Bruker SMART 1000 CCD area
detector25 with graphite monochromated Mo-Kα radiation (λ = 0.71073 Å). The structures
were refined with SHELXL-9726 by full matrix least squares on F2. The positions of the
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.27
Spectroscopic Measurements
1H, 13C, and 31P NMR spectra were recorded with a Bruker Avance DRS 500 spec-
1
trometer. H and 13C chemical shifts are given relative to internal TMS, 31P chemical
shifts relative to 85% H3PO4 as external standard. Infrared (IR) spectra were recorded
with 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.
Synthesis of compounds 1–4: General Procedure
To a solution of 10 mmol 2,4-dichloro-N-benzoyl phosphoramidic dichloride28 in dry
acetonitrile, 10 mmol of the corresponding diamine, and 20 mmol of N(C2H5)3 were added

SPECTROSCOPY AND STRUCTURE OF NEW 1,3,2-DIAZAPHOSPHOLES
189
dropwise at 0◦C and the mixture was stirred for 10 h. Then, the solvent was evaporated and
the residue was washed with distilled water and dried.
2-(2,4-Dichloro-N-benzoyl)-1,3,2-diazaphosphole-2-oxide (1). Yield: 74%;
mp = 200.3◦C. Elemental analysis: Calcd: C, 36.73; H, 3.40; N, 14.28. Found: C, 36.71; H,
3.42; N, 14.25%. IR (KBr, cm−1): 3360 (m, NH), 3085 (m), 2960 (m), 1660 (s, C=O), 1578
(m), 1469 (m), 1436 (vs), 1369 (w), 1262 (s), 1202 (s, P=O), 1131 (w), 1094 (m), 1070
(m), 1045 (m, P–Namine), 917 (m, P–Namide), 893 (m), 866 (m), 835 (m), 807 (m), 769 (m),
1
744 (m), 699 (w), 581 (m), 483 (m), 432 (m). H NMR (500.13 MHz, D6-DMSO, 25◦C,
TMS): δ = 3.18 (m, 2H, CH2), 3.34 (m, 2H, CH2), 4.73 (d, 2JPNH = 12.8 Hz, 2H, NHamine),
2
7.45 (m, 2H, arom-H), 7.64 (s, 1H, arom-H), 9.35 (d, JPNH = 5.5 Hz, 1H, NHamide). 13
C
NMR (125.76 MHz, D6-DMSO, 25◦C, TMS): δ = 40.9 (s, CH2), 41.0 (s, CH2), 127.0 (s),
129.0 (s), 130.2 (s), 131.0 (s), 134.5 (s), 135.5 (d, 3JPC = 8.7 Hz, Cipso), 167.1 (s, C=O).
31P NMR (202.46 MHz, D6-DMSO, 25◦C, H3PO4 external): δ = 21.0.
1,3-Dimethyl-2-(2,4-dichloro-N-benzoyl)-1,3,2-diazaphosphole-2-oxide
(2). Yield: 95%; mp = 219.2◦C. Elemental analysis: Calcd.: C, 40.99; H, 4.35; N, 13.04.
Found: C, 40.98; H, 4.37; N, 13.03. IR (KBr, cm−1): 3090 (s), 2860 (s), 1679 (s, C=O),
1576 (ms), 1468 (s), 1437 (vs), 1378 (mw), 1279 (s), 1249 (s), 1209 (vs, P=O), 1160 (vs),
1122 (s), 1099 (s), 1032 (s, P–Namine), 941 (s, P–Namide), 872 (s), 814 (m), 772 (ms), 750
(s), 693 (m), 659 (mw), 567 (w), 499 (ms), 434 (ms). 1H NMR (500.13 MHz, D6-DMSO,
25◦C, TMS): δ = 2.51 (s, 6H, CH3), 3.16 (m, 2H, CH2), 3.30 (m, 2H, CH2), 7.45 (m,
2H, arom-H), 7.66 (s, 1H, arom-H), 9.50 (d, JPNH = 6.0 Hz, 1H, NHamide). 13C NMR
2
(125.76 MHz, D6-DMSO, 25◦C, TMS): δ = 30.6 (d, 2JPC = 5.2 Hz, CH3), 46.3 (d, 2JPC
=
14.2 Hz), 127.2 (s), 129.0 (s), 130.1 (s), 130.7 (s), 134.7 (s), 135.3 (d, 3JPC = 8.7 Hz, Cipso),
167.5 (s, C=O). 31P NMR (202.46 MHz, D6-DMSO, 25◦C, H3PO4 external): δ = 17.3.
2-(2,4-Dichloro-N-benzoyl)-1,3,2-diazaphosphorinane-2-oxide (3). Yield:
75%; mp = 177.9◦C. Elemental analysis: Calcd: C, 31.58; H, 3.16; N, 11.05. Found: C,
31.56; H, 3.17; N, 11.03. IR (KBr, cm−1): 3335 (m, NH), 3230 (m, NH), 2915 (m), 1671
(s, C=O), 1578 (m), 1465 (m), 1434 (s), 1378 (w), 1340 (w), 1280 (m), 1239 (w), 1216
(w), 1165 (s, P=O), 1118 (w), 1092 (s), 1044 (m), 1011 (m, P–Namine), 956 (w), 886 (m,
P–Namide), 855 (m), 776 (m), 736 (w), 701 (w), 663 (w), 629(w), 570 (m), 496 (m), 437
(m), 407 (m). 1H NMR (500.13 MHz, D6-DMSO, 25◦C, TMS): 1.59 (m, 2H, CH2), 3.11
(m, 4H, CH2), 4.62 (s, 2H, NHamine), 7.49 (m, 2H, arom-H), 7.69 (s, 1H, arom-H), 9.43
3
(b, 1H, NHamide). 13C NMR (125.76 MHz, D6-DMSO, 25◦C, TMS): δ = 26.1 (d, JPC
=
6.1 Hz, CH2), 41.6 (d, 2JPC = 3.0 Hz, CH2), 127.2 (s), 129.0 (s), 130.0 (s), 130.2 (s), 134.6
(s), 135.5 (d, 3JPC = 8.1 Hz, Cipso), 167.7 (s, C=O). 31P NMR (202.46 MHz, D6-DMSO,
25◦C, H3PO4 external): δ = 3.3.
5,5-Dimethyl-2-(2,4-dichloro-N-benzoyl)-1,3,2-diazaphosphorinane-2-
oxide (4). Yield: 83%; mp = 179.1◦C. Elemental analysis: Calcd: C, 43.90; H, 4.88; N,
12.80. Found: C, 43.89; H, 4.89; N, 12.82%. IR (KBr, cm−1): 3455 (m, NH), 3345 (s, NH),
3225 (s), 3095 (w), 2955 (m), 1669 (s, C=O), 1590 (m), 1473 (s), 1433 (s), 1379 (m),
1344 (m), 1307 (w), 1280 (m), 1247 (w), 1185 (s, P=O), 1136 (m), 1097 (s, P–Namine),
1048 (w), 956 (m, P–Namide), 878 (m), 844 (m), 821 (m), 774 (m), 701 (m), 669 (w), 577
1
(m), 523 (w), 490 (m), 435 (m). H NMR (500.13 MHz, D6-DMSO, 25◦C, TMS): 0.76
3
2
3
(s, 3H, CH3), 1.07 (s, 3H, CH3), 2.57 (ddd, JHH = 5.6 Hz, JHH = 11.9 Hz, JPNCH
=
2
26.7 Hz, 2H, CH2), 2.98 (d, JHH = 12.3 Hz, 2H, CH2), 4.62 (s, 2H, NHamine), 7.47
(m, 2H, arom-H), 7.66 (s, 1H, arom-H), 9.42 (b, 1H, NHamide). 13C NMR (125.76 MHz,
D6-DMSO, 25◦C, TMS): δ = 22.9 (s, CH3), 24.8 (s, CH3), 30.1 (d, 3JPC = 4.7 Hz, CH2),
52.9 (d, 2JPC = 1.8 Hz, CH2), 127.2 (s), 129.0 (s), 130.2 (s), 130.8 (s), 134.6 (s), 135.5 (d,

190
K. GHOLIVAND ET AL.
3JPC = 8.0 Hz, Cipso), 167.7 (s, C=O). 31P NMR (202.46 MHz, D6-DMSO, 25◦C, H3PO4
external): δ = 1.1.
CONCLUSION
The synthesis, spectroscopic, and structural characterization of new diazaphospholes
and diazaphosphorinanes has been performed. The structure of compound 2 showed a three
dimensional polymeric chain in the crystalline lattice by intermolecular strong N–H···O and
weak C–H···O and C–H···Cl hydrogen bonds. The phosphorus atoms are more deshielded in
diazaphospholes than in diazaphosphorinanes. The 13C NMR spectrum of 2 reveals a larger
2JPC(aliphatic) value for endocyclic carbon atom (14.2 Hz) than for the exocyclic CH3 carbon
2
atom (5.2 Hz). Furthermore, for diazaphosphorinanes 3JPC(aliphatic) ≈ 2 × JPC(aliphatic)
.
SUPPLEMENTARY INFORMATION
Crystallographic data for the structure of compound 2 have been deposited with the
Cambridge Crystallographic Data Center as supplementary publication no. CCDC 709121.
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; E-mail: deposit@ccdc.cam.ac.uk
or www: http://www.ccdc.cam.ac.uk).
REFERENCES
1. Prasad, S. B.; Rosangkima, G.; Nicol, B. M. Eur. J. Pharmacol. 2010, 645, 47–54.
2. Cigni, A.; Faedda, R.; Maddalena Atzeni, M.; Pileri, P. V.; Alagna, S.; Rovasio, P.; Satta, A. Er.;
Loi, M. R.; Sini, A.; Satta, V.; Masala, A. Am. J. Kidney Dis. 2008, 52, 887–896.
3. Varshney, L.; Dodke, P. B. Rad. Phys. Chem. 2004, 71, 1103–1111.
4. Baumann, F.; Preiss, R. J. Chromatogr. B: Biomed. Sci. Appl. 2001, 764, 173–192.
5. Ishida, T.; Shiraga, E.; Kiwada, H. J. Control. Release 2009, 134, 194–200.
6. Manegold, C.; Bischoff, H.; Fischer, J. R.; Peukert, M.; Schma¨hl, A.; Drings, P. Lung Cancer
1990, 6, 203–204.
7. De la Cruz, A.; Koeller, K. J.; Rath, N. P.; Spilling, C. D.; Vasconcelos, I. C. F. Tetrahedron
1998, 54, 10513–10524.
8. Khusainova, N. G.; Mostovaya, O. A.; Azancheev, N. M.; Litvinov, I. A.; Krivolapov, D. B.;
Cherkasov, R. A. Mendeleev Commun. 2004, 14, 212–214.
9. Bansal, R. K.; Karaghiosoff, K.; Gupta, N.; Gandhia, N.; Kumawat, S. K. Tetrahedron 2005, 61,
10521–10528.
10. Edwards, P. G.; Kariuki, B.; Newman, P. D. Polyhedron 2011, 30, 935–941.
11. Streubel, R.; Schiemann, U.; Hoffmann, N.; Schiemann, Y.; Jones, P. G.; Gudat, D.
Organometallics 2000, 19, 475–481.
12. Delangle, P.; Dutasta, J.-P.; Van Oostenryck, L.; Tinant, B.; Declercq, J.-P. J. Org. Chem. 1996,
61, 8904–8914.
13. Barendt, J. M.; Bent, E. G.; Haltiwanger, R. C.; Squier, C. A.; Norman, A. D. Inorg. Chem. 1989,
28, 4425–4427.
14. Bent, E. G.; Schaeffer, R.; Haltiwanger, R. C.; Norman, A. D. Inorg. Chem. 1990, 29, 2608–2613.
15. Gholivand, K.; Pourayoubi, M.; Shariatinia, Z. Polyhedron 2007, 26, 837–844.
16. Gholivand, K.; Shariatinia, Z.; Pourayoubi, M.; Farshadian, S. Z. Naturforsch. 2005, 60b,
1021–1026.
17. Gholivand, K.; Shariatinia, Z.; Ansar, S.; Mashhadi, S. M.; Daeepour, F. Struct. Chem. 2009, 20,
481–488.

SPECTROSCOPY AND STRUCTURE OF NEW 1,3,2-DIAZAPHOSPHOLES
191
18. Gholivand, K.; Shariatinia, Z.; Afshar, F.; Faramarzpour, H.; Yaghmaian, F. Main Group Chem.
2007, 6, 231–248.
19. Gholivand, K.; Shariatinia, Z.; Mahzouni, H. R.; Amiri, S. Struct. Chem. 2007, 18, 653–660.
20. Gholivand, K.; Ghadimi, S.; Forouzanfar, A.; Naderimanesh, H. Magn. Reson. Chem. 2001, 39,
684–688.
21. Gholivand, K.; Shariatinia, Z.; Pourayoubi, M. Z. Anorg. Allg. Chem. 2005, 631, 961–967.
22. Gholivand, K.; Pourayoubi, M.; Shariatinia, Z.; Mostaanzadeh, H. Polyhedron 2005, 24, 655–662.
23. Gholivand, K.; Shariatinia, Z. Struct. Chem. 2007, 18, 95–102.
24. Corbridge, D. E. C. Phosphorus, an Outline of Its Chemistry, Biochemistry and Technology, 5th
Ed., Elsevier: the Netherlands, 1995, Chapter 1.
25. Bruker, SMART. Bruker Molecular Analysis Research Tool, v. 5.059. Bruker AXS: Madison,
Wisconsin, USA, 1998.
26. Sheldrick, G. M.; SHELXTL v. 5.10, Structure Determination Software Suit, Bruker AXS:
Madison, WI, USA, 1998.
27. Sheldrick, G. M. SADABS v. 2.01, Bruker/Siemens Area Detector Absorption Correction Pro-
gram, Bruker AXS: Madison, WI, USA, 1998.
28. Gholivand, K.; Oroujzadeh, N.; Shariatinia, Z. Heteroatom Chem. 2010, 21, 168–180.