Synthesis and crystal structure of 2-propyl-5-phenyl-1, 4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino [1,2-a][1,3,2]benzodiazaphosphorine 3-oxide

Article abstract of DOI:10.1023/A:1015683720074

The synthesis and structure characterization of 2-propyl-5-phenyl-1,4-dioxo-1,2,3,4,5, 6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a][1,3,2]benzodiazaphosphorine 3-oxide are described. The title compound has been designed to incorporate proximate carbonyl and phosphoryl groups in a heterocycle fused to benzophosphadiamide heterocycle. Crystal data: C₁₉H₂₀N₃O₃P, Monoclinic, space group P2(1)/c, with a = 9.7585(9) A, b = 21.4319(19) A, c= 17.7900(16) A, β = 100.823(2)°, Z = 8, V = 3654.5(6) A³. The crystal structure shows that the proximate carbonyl and phosphoryl groups are not coplanar, and the [1,4,2]diazaphosphorino moiety prefers the boat conformation.

Full text of DOI:10.1023/A:1015683720074

C
Journal of Chemical Crystallography, Vol. 31, Nos. 9–10, October 2001 ( 2002)
Synthesis and crystal structure of 2-propyl-5-phenyl-1,
4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino
[1,2-a][1,3,2]benzodiazaphosphorine 3-oxide
Junmin Huang,(1) Hui Chen,(2) and Ruyu Chen(1)
Received April 16, 2001
The synthesis and structure characterization of 2-propyl-5-phenyl-1,4-dioxo-1,2,3,4,5,
6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a][1,3,2]benzodiazaphosphorine 3-oxide are
described. The title compound has been designed to incorporate proximate carbonyl and
phosphoryl groups in a heterocycle fused to benzophosphadiamide heterocycle. Crys-
˚
tal data: C19H20N3O3P, Monoclinic, space group P2(1)/c, with a = 9.7585(9) A, b =
3
˚
˚
˚
21.4319(19) A, c = 17.7900(16) A, = 100.823(2) , Z = 8, V = 3654.5(6) A . The crys-
tal structure shows that the proximate carbonyl and phosphoryl groups are not coplanar,
and the [1,4,2]diazaphosphorino moiety prefers the boat conformation.
KEY WORDS: Crystal structure; [1,4,2]diazaphosphorino[1,2-a][1,3,2]benzodiazaphosphorine.
Introduction
possess antitumor activity, and have also received
an increasingly wide interest in chemistry,
medicine, and agricultural science.13–16 As a part
of our ongoing program aimed at searching for
novel antitumor and antiviral agents with high
activity and low toxicity, 2-propyl-5-phenyl-1,
4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diaza-
phosphorino [1,2-a] [1,3,2] benzodiazaphospho-
rine 3-oxide was designed to incorporate the
proximate carbonyl and phosphoryl groups in
a heterocycle fused to benzophosphadiamide
heterocycle, and synthesized in good yield, as
shown in Scheme 1, and its crystal structure
is reported here, which contains the proximate
carbonyl and phosphoryl groups in the fused
heterocycle.
During the past two decades, -ketophos-
phonates and their derivatives have attracted
considerable attention because these compounds
are endowed with special physical, chemical, and
pharmacological properties due to the proximity
of the carbonyl and the phosphoryl groups.1–12 In
the study on new pharmaceuticals and agrochem-
icals, the application of heterocycles is suggested
to improve the biological activity. A sizeable
number of endogenous compounds that play a
key role in regulation of various life processes
consists of fused heterocycles. Moreover, benzo-
fused and related analogs of cyclophosphamide
(1) Institute of Elemento-Organic Chemistry, Nankai University,
Tianjin 300071, People’s Republic of China.
(2) Procter & Gamble Technology (Beijing) Co., Ltd., Beijing,
People’s Republic of China.
To whom correspondence should be addressed. E-mail:
jmhuang@public.tpt.tj.cn.
There has been a considerably growing inter-
est in heterocyclic compounds due to their phar-
maceutical importance and extensive application
inorganicsynthesis.17 Efficientmethodologiesfor
forming the bond connecting the carbonyl and
445
C
1074-1542/01/1000-0445/0 2002 Plenum Publishing Corporation

446
Huang, Chen, and Chen
Scheme 1.
1
1
the phosphoryl groups are available in the ar-
senal of the synthetic chemist.1,18 However, to
the best of our knowledge, very few fused het-
erocycles bearing the proximate carbonyl and
phosphoryl groups in the heterocyclic structure
are so far reported. According to the capabil-
ity of possible cyclization between the amido
functionality and the bromoethyl group forming
the proximate carbonyl and phosphoryl groups
in the fused heterocyclic structure, the method
as shown in scheme 1 was to reflux the mixture
of the 1-(2-bromoethyl)-3-propyl-2,3-dihydro-
1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide
containing a P H bond with phenyl isocyanate in
toluene with the presence of triethylamine, which
involved an addition reaction to form the amido
functionality and the bromoethyl group in the
same molecule and subsequent intramolecular cy-
clization between the two groups in a one-pot
procedure.
in wavenumbers (cm ). The H and 31P NMR
spectra were recorded on a BRUKER AC-P200
instrument. Tetramethylsilane (TMS) was used
as an internal standard for H NMR, and 85%
1
phosphoric acid (H3PO4) was used as an exter-
nal standard for 31P NMR spectroscopy. The nu-
clei that are deshielded relative to their respec-
tive standards are assigned a positive chemical
shift. Coupling constants, J, are given in Hertz.
Mass spectra were recorded on a Hewlett-Packard
5988 instrument. Elemental analyses were car-
ried out on a Yana MT-3 instrument. Column
chromatography was performed using silica gel
H (10–40 m, Haiyang Chemical Factory of
Qingdao).
1-(2-Bromoethyl)-3-propyl-2,3-dihydro-1,
3,2-benzodiazaphosphorin-4(1H)-one
2-oxide
was prepared according to reported methods9,16
by the multistep route outlined in Scheme 2. The
experimental data of this intermediate are:
1
49.2% overall yield, m.p. 82–84 C. H NMR
(CDCl3/TMS, ppm; J, Hz): 0.96 (t, 3H, NCH2
Experimental
3
CH2CH3, JHH = 7.4), 1.77 (m, 2H, NCH2
Melting points were determined using a
YANACO MP-500 apparatus and are uncorrected.
IR spectra were recorded on a SHIMADZU-435
spectrometer, and the band positions are reported
CH2CH3), 3.55–3.85 (m, 4H, PNCH2CH2CH3+
PNCH2CH2Br), 4.15 (m, 2H, PNCH2CH2Br),
6.90–8.32 (m, 4H, C6H4), 7.86 (d, 1H,
P(O)H,1 JPH = 645.9). 31P NMR (CDCl3,
Scheme 2.

Synthesis and crystal structure of title compound
447
Table 1. Crystallographic Data for the 2-Propyl-5-phenyl-1,
4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a]
[1,3,2]benzodiazaphosphorine 3-Oxide
ppm): 5.95. Anal. calcd. for C12H16BrN2O2P:
C, 43.52; H, 4.87; N, 8.46. Found: C, 43.68; H,
5.05; N, 8.66.
Empirical formula
CCDC deposit
Color
Crystal size, mm
Crystal system
Space group
C19H20N3O3P
CCDC-1003/6076
Colorless
0.10 0.15 0.20
Monoclinic
Preparation of 2-propyl-5-phenyl-1,
4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]
diazaphosphorino[1,2-a][1,3,2]
P 2(1)/c
benzodiazaphosphorine 3-oxide
˚
Unit-cell dimensions
a = 9.7585(9) A
˚
˚
b = 21.4319(19) A
c = 17.7900(16) A
A mixture of 1-(2-bromoethyl)-3-propyl-
2,3-dihydro-1,3,2-benzodiazaphosphorin-4(1H)-
one 2-oxide (0.99 g, 3 mmol), phenyl isocyanate
(0.36 g, 3 mmol), triethylamine (0.61 g, 6 mmol),
and 30 mL dry toluene was heated at reflux for
8 h and the produced triethylamine hydrobromide
was filtered off. The solvent from the filtrate was
removed under reduced pressure and the residue
was chromatographed on a column of silica
gel using a mixture of 40% ethyl acetate/light
petroleum (b.p. 60–90 C) to elute the product.
The single crystals suitable X-ray analysis were
obtained by recrystallization from a mixture
of ethyl acetate and petroleum ether (b.p. 90–
120 C), yield 0.78 g (70.4%), m.p. 152–154 C.
Anal. calcd. for C19H20N3O3P: C, 61.79; H,
5.46; N, 11.38. Found C, 61.52; H, 5.35; N,
= 100.823(2)
3
˚
Volume, A
3654.5(6)
8
369.35
1.343
0.175
1552
Z
Formula weight
3
Density
, Mg m
calc.
1
Absorption coefficient, mm
F(000)
Diffractometer/scan
Radiation/wavelength
SMART CCD 1000
Mo K (graphite mono
chrom.)/0.71073 A
˚
Temperature, K
range for data collection, deg
Scan type
298
2
2.23–25.03
ω
Index ranges
11
h
8, 25
24, 17
15,024
k
l
21
Reflections measured
Independent/observed
reflections
Absorption correction
Refinement method
6410(R = 0.0309)
int
([I 2 (I )])
SADABS
Full-matrix least-squares
on F2
1
Data/restraints/parameters
Weight
6410/0/469
11.16. IR (KBr, cm ): 2950.5, 1669.1, 1643.4 (s,
1/[ 2(Fo2) + (0.0984P)2+
C O); 1602.7 (s, C O); 1486.6, 1398.0, 1346.2
(s, P O), 1236.7, 1213.9, 1034.0 (m, P N);
939.4, 904.7, 758.5, 701.8. EI-MS (m/z, %): 369
(7.5); 341 (41.6); 326, 312, 299 (93.2); 284,
258, 235, 207, 194, 180, 152, 132 (47.5); 104
0.7604P]
P = (Fo2 + 2Fc2)/3
1.026
R1 = 0.0534, wR2 = 0.1455
R1 = 0.0776, wR2 = 0.1657
0.844/ 0.473
Goodness of fit on F2
Final R indices [I > 2 (I )]
R indices (all data)
Largest diff. peak and hole,
1
3
˚
(69.8); 77 (100). H NMR (CDCl3/TMS, ppm;
e A
3
J, Hz): 0.96 (t, 3H, NCH2CH2CH3, JHH
=
7.4), 1.88 (m, 2H, PNCH2CH2CH3, 3.60–4.15
(m, 5H, PNCH2CH2CH3 + PNCH2CH2N +
listed in Table 1. Data were collected with
a SMART CCD 1000 area detector, using
graphite monochromatized Mo K radiation ( =
1/2
PNCH2CH2N), 4.96 (m, 1H, 1/2
PNCH2CH2N), 6.92–8.35 (m, 9H, C6H5 + C6H4.
˚
0.71073 A). The structure was solved by direct
31P NMR (CDCl3/H3PO4, ppm): 7.74 (s).
methods using SHELXS-97 package and refined
on F2 using the data (I > 2 (I)) by full-matrix
least-square procedures using SHELXL-97. All
non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were located from difference
maps and then added geometrically, included in
the refinement, with Uiso fixed to 1.2 times Ueq of
Crystal structure determinations
and refinements
The crystal data, data collection, and re-
finement parameters for the title compound are

448
Huang, Chen, and Chen
Table 2. Atomic Coordinates (104) and Equivalent Isotropic
their parent atoms, but restrained to ride on their
parent atoms. The fractional coordinates of non-
hydrogen atoms and equivalent isotropic thermal
parameters are given in Table 2, and the bond
lengths and bond angles are listed in Tables 3
and 4, respectively.
The crystal structure of 2-propyl-5-phenyl-1,
4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaph-
phosphorino[1,2-a][1,3,2]benzodiazaphosphorine
3-oxide is shown in Figs. 1 and 2. Figure 1 is a
perspective view of the compound showing the
atomic numbering scheme, and Fig. 2 depicts the
molecular packing in the unit cell.
2
Displacement Coefficients (103 A ) for the 2-Propyl-5-phenyl-1,
˚
4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a]
[1,3,2]benzodiazaphosphorine 3-Oxide
a
Atom
x
y
z
Ueq
P(1)
4522(1)
5042(3)
5091(2)
5806(2)
3055(2)
6219(2)
6010(3)
5664(3)
5011(3)
5337(3)
5554(3)
5765(4)
6246(5)
6518(5)
6321(4)
5837(3)
5656(3)
6690(3)
7576(3)
8448(4)
8425(4)
7541(4)
6661(3)
4680(4)
3339(4)
2981(6)
3059(1)
2893(1)
2459(1)
3709(1)
3247(1)
4059(1)
2293(1)
3697(1)
3242(1)
2575(1)
1893(1)
1378(2)
821(2)
9465(1)
8651(1)
10023(1)
10692(1)
9362(1)
9535(1)
7840(1)
9920(2)
11048(2)
10857(2)
9765(2)
10249(2)
10003(3)
9280(3)
8798(2)
9028(2)
8466(2)
11158(1)
11806(2)
12252(2)
12042(2)
11409(2)
10960(2)
8031(2)
7491(2)
6866(2)
41(1)
48(1)
43(1)
41(1)
55(1)
52(1)
82(1)
41(1)
45(1)
47(1)
48(1)
64(1)
83(1)
90(1)
72(1)
52(1)
53(1)
42(1)
55(1)
73(1)
72(1)
62(1)
50(1)
59(1)
78(1)
101(2)
N(1)
N(2)
N(3)
O(1)
O(2)
O(3)
C(1)
C(2)
C(3)
C(4)
C(5)
Results and discussion
C(6)
C(7)
759(2)
C(8)
1263(2)
1831(1)
2342(2)
4149(1)
3943(2)
4374(2)
4992(2)
5190(2)
4776(1)
3362(2)
3218(2)
3695(2)
The crystal structure of 2-propyl-5-phenyl-1,
4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaph-
osphorino [1,2-a ][1,3,2 ] benzodiazaphosphorine
3-oxide contains two molecules in the asymmetric
unit. The torsion angles between the P O and
C O groups are 97.2(2) and 91.2(3) , indicat-
ing that the proximate carbonyl and phosphoryl
groups are not coplanar. Consequently there
is a fused heterocycle tension and then de-
stroy conjugation between the C O and the
P O moieties. The P C bond lengths are
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
P(2)
519(1)
1727(2)
1789(2)
125(5)
30(3)
2865(1)
2702(1)
2719(1)
1800(2)
2295(1)
3460(1)
3713(1)
3101(1)
4080(1)
4093(1)
3404(1)
3898(2)
3841(2)
3296(2)
2803(2)
2839(2)
2283(2)
3996(1)
3782(2)
4073(2)
4578(2)
4791(2)
4495(1)
1689(2)
1492(2)
773(2)
9756(1)
10095(1)
10842(1)
8136(2)
9258(2)
9156(1)
10703(1)
10529(2)
10345(2)
9486(2)
8356(2)
7883(2)
7095(2)
6766(2)
7221(2)
8021(2)
8456(2)
11306(2)
12042(2)
12608(2)
12442(2)
11708(2)
11132(2)
9657(3)
9667(3)
9853(4)
46(1)
64(1)
60(1)
129(1)
60(1)
46(1)
45(1)
45(1)
50(1)
50(1)
50(1)
66(1)
78(1)
79(1)
76(1)
61(1)
80(1)
44(1)
62(1)
79(1)
72(1)
61(1)
49(1)
88(1)
101(1)
181(4)
O(4)
O(5)
˚
˚
1.851(3) A and 1.852(3) A, which are close to
O(6)
˚
N(4)
the P C single bond distance (1.80–1.85 A).
N(5)
645(2)
916(2)
937(3)
304(3)
527(3)
842(3)
1320(4)
1496(4)
1195(4)
740(4)
546(4)
105(5)
1919(3)
2082(4)
3023(4)
3779(4)
3616(3)
2697(3)
374(5)
1762(5)
1868(9)
All the N atoms are sp2 hybridized. The bond
lengths of N(2) C(4), N(1) C(10), N(5)
C(23), and N(4) C(29) (1.402(3), 1.392(4),
N(6)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
˚
1.406(4), and 1.408(5) A, respectively) lie
halfway between the length of a C N bond with
both atoms in sp2 hybridization of bond order
19
˚
˚
1.0 (1.45 A) and bond order 1.5 (1.39 A). This
reveals that the atoms of N(2), C(4), C(5), C(6),
C(7), C(8), C(9), C(10), and N(1) form a delo-
calized system, and the delocalized system
is also formed by the atoms N(5), C(23), C(24),
C(25), C(26), C(27), C(28), C(29), and N(4).
As shown in Table 5, the plane defined by
N(2), C(4), C(5), C(6), C(7), C(8), C(9), and C(10)
atoms is coplanar within an average deviation of
˚
0.0053 A. At the same time, P(1) and N(1) atoms
P P
aUeq = (1/3)
j Ui j ai aj ai aj .
i
are on the same side of the coplanar structure with

Synthesis and crystal structure of title compound
449
˚
Table 3. Bond Lengths (A) for the 2-Propyl-5-phenyl-1,4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a]
[1,3,2]benzodiazaphosphorine 3-Oxide
P(1) O(1)
P(1) C(1)
1.466(2)
1.851(3)
1.402(3)
1.433(3)
1.231(4)
1.396(4)
1.369(6)
1.378(4)
1.374(5)
1.502(5)
P(1) N(2)
N(1) C(10)
N(2) C(3)
N(3) C(2)
C(2) C(3)
C(5) C(6)
C(8) C(9)
C(11) C(16)
C(14) C(15)
C(18) C(19)
1.654(2)
1.392(4)
1.480(4)
1.479(3)
1.516(4)
1.384(5)
1.395(4)
1.387(4)
1.352(5)
1.502(6)
P(1) N(1)
N(1) C(17)
N(3) C(1)
O(2) C(1)
C(4) C(5)
C(6) C(7)
C(9) C(10)
C(12) C(13)
C(15) C(16)
1.660(2)
1.485(4)
1.355(3)
1.226(3)
1.392(4)
1.367(6)
1.470(5)
1.398(5)
1.380(4)
N(2) C(4)
N(3) C(11)
O(3) C(10)
C(4) C(9)
C(7) C(8)
C(11) C(12)
C(13) C(14)
C(17) C(18)
P(2) O(4)
1.465(2)
1.852(3)
1.408(5)
1.474(4)
1.470(4)
1.403(4)
1.354(6)
1.368(4)
1.373(5)
1.416(6)
P(2) N(5)
1.653(2)
1.223(3)
1.488(4)
1.349(4)
1.503(4)
1.384(5)
1.403(5)
1.379(4)
1.365(5)
1.577(7)
P(2) N(4)
1.655(3)
1.223(4)
1.406(4)
1.442(4)
1.379(5)
1.364(6)
1.442(5)
1.378(5)
1.383(4)
P(2) C(20)
N(4) C(29)
N(5) C(22)
N(6) C(21)
C(23) C(28)
C(26) C(27)
C(30) C(31)
C(32) C(33)
C(36) C(37)
O(5) C(20)
N(4) C(36)
N(6) C(20)
C(21) C(22)
C(24) C(25)
C(27) C(28)
C(30) C(35)
C(33) C(34)
C(37) C(38)
O(6) C(29)
N(5) C(23)
N(6) C(30)
C(23) C(24)
C(25) C(26)
C(28) C(29)
C(31) C(32)
C(34) C(35)
Table 4. Bond Angles (deg) for the 2-Propyl-5-phenyl-1,4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a]
[1,3,2]benzodiazaphosphorine 3-Oxide
O(1) P(1) N(2)
O(1) P(1) C(1)
C(10) N(1) C(17)
C(4) N(2) C(3)
C(1) N(3) C(11)
O(2) C(1) N(3)
N(3) C(2) C(3)
C(5) C(4) N(2)
C(7) C(6) C(5)
C(8) C(9) C(4)
O(3) C(10) N(1)
119.94(12)
110.15(12)
116.8(2)
118.2(2)
122.3(2)
125.6(3)
113.1(2)
120.2(3)
121.2(4)
119.6(3)
119.5(3)
O(1) P(1) N(1)
N(2) P(1) C(1)
C(10) N(1) P(1)
C(4) N(2) P(1)
C(1) N(3) C(2)
O(2) C(1) P(1)
N(2) C(3) C(2)
C(9) C(4) N(2)
C(6) C(7) C(8)
C(8) C(9) C(10)
O(3) C(10) C(9)
C(12) C(11) N(3)
113.67(12)
101.82(12)
127.1(2)
124.66(19)
117.3(2)
121.1(2)
112.5(2)
121.5(3)
119.0(3)
117.1(3)
122.3(3)
119.1(2)
N(2) P(1) N(1)
N(1) P(1) C(1)
C(17) N(1) P(1)
C(3) N(2) P(1)
C(11) N(3) C(2)
N(3) C(1) P(1)
C(5) C(4) C(9)
C(6) C(5) C(4)
C(7) C(8) C(9)
C(4) C(9) C(10)
N(1) C(10) C(9)
C(16) C(11) N(3)
103.55(12)
106.35(12)
115.8(2)
116.36(17)
120.4(2)
113.31(19)
118.3(3)
120.5(3)
121.4(4)
123.3(3)
118.2(3)
120.7(2)
C(12) C(11) C(16) 120.2(3)
C(11) C(12) C(13) 118.8(3)
C(14) C(15) C(16) 120.7(3)
C(17) C(18) C(19) 112.8(4)
C(14) C(13) C(12) 120.4(3)
C(15) C(16) C(11) 119.7(3)
C(15) C(14) C(13) 120.2(3)
N(1) C(17) C(18)
113.2(3)
O(4) P(2) N(5)
118.79(14)
108.91(13)
115.9(3)
117.9(2)
122.9(2)
125.7(3)
113.6(2)
121.2(3)
O(4) P(2) N(4)
N(5) P(2) C(20)
C(29) N(4) P(2)
C(23) N(5) P(2)
C(20) N(6) C(21)
O(5) C(20) P(2)
N(5) C(22) C(21)
C(28) C(23) N(5)
114.30(13)
102.86(12)
125.3(2)
124.6(2)
117.9(2)
121.1(2)
112.0(2)
120.3(3)
N(5) P(2) N(4)
N(4) P(2) C(20)
C(36) N(4) P(2)
C(22) N(5) P(2)
C(30) N(6) C(21)
N(6) C(20) P(2)
C(24) C(23) C(28) 118.5(3)
C(23) C(24) C(25) 120.9(3)
C(26) C(27) C(28) 121.9(4)
C(23) C(28) C(29) 123.3(3)
102.48(13)
108.56(14)
117.1(2)
117.53(19)
118.6(2)
O(4) P(2) C(20)
C(29) N(4) C(36)
C(23) N(5) C(22)
C(20) N(6) C(30)
O(5) C(20) N(6)
N(6) C(21) C(22)
C(24) C(23) N(5)
113.2(2)
C(26) C(25) C(24) 121.0(4)
C(27) C(28) C(23) 118.7(3)
C(27) C(26) C(25) 119.0(3)
C(27) C(28) C(29) 118.0(3)
O(6) C(29) N(4)
119.9(4)
O(6) C(29) C(28)
C(31) C(30) N(6)
C(33) C(32) C(31) 120.8(3)
C(30) C(35) C(34) 119.9(3)
120.7(3)
120.7(3)
N(4) C(29) C(28)
C(35) C(30) N(6)
C(34) C(33) C(32) 119.9(3)
C(37) C(36) N(4) 113.3(4)
119.4(3)
119.0(3)
C(31) C(30) C(35) 120.2(3)
C(30) C(31) C(32) 119.3(3)
C(33) C(34) C(35) 119.9(3)
C(36) C(37) C(38) 108.6(5)

450
Huang, Chen, and Chen
Fig. 1. ORTEP of the 2-Propyl-5-phenyl-1,4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]
diazaphosphorino[1,2-a][1,3,2]benzodiazaphosphorine 3-Oxide.
˚
a distance of 0.2744 and 0.1482 A, respectively.
In another molecule of the asymmetric unit, the
plane defined by N(5), C(23), C(24), C(25), C(26),
C(27), C(28), and C(29) atoms is also coplanar
P(1) atoms of the [1,4,2]diazaphosphorino moiety
are in a boat conformation. The coplanar C(1),
C(3), N(2), and N(3) atoms, within an average
˚
deviation of 0.0102 A, form the ground floor of
˚
within an average deviation of 0.0168 A, and
forms a 17.25(0.09) dihedral angle with the for-
mer plane. The C(1), C(2), C(3), N(2), N(3), and
the boat conformation. Meanwhile, P(1) and C(2)
atoms are on the same side of the planar with a
˚
distance of 0.7067 and 0.6315 A, respectively.
Table 5. The Least-Squares Planes for the 2-Propyl-5-phenyl-1,4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]
diazaphosphorino[1,2-a][1,3,2]benzodiazaphosphorine 3-Oxide
Plane equation: 8.7655(0.0044)x + 6.1840(0.0197)y + 2.7922(0.0185)z = 8.7728(0.0156)
Atoms
N2
9.4
C4
6.8
C5
5.6
C6
2.2
C7
1.2
C8
5.6
C9
3.3
C10
2.6
P1
274.4
N1
148.2
3
˚
Dist. (10 A)
Plane equation: 9.5215(0.0026)x 4.4115(0.0200)y 1.9512(0.0323)z = 1.8166(0.0328)
Atoms
Dist. (10 A)
C3
10.2
N2
9.3
C1
10.2
N3
11.1
C2
631.5
P1
706.7
3
˚
Plane equation: 9.3349(0.0037)x 6.1946(0.0260)y + 2.5442(0.0162)z = 0.8063(0.0158)
Atoms
N5
C23
3.5
C24
16.2
C25
16.2
C26
11.2
C27
14.5
C28
14.7
C29
29.1
P2
385.3
N4
99.0
3
˚
Dist. (10 A)
17.6
Plane equation: 8.9468(0.0040)x 3.1679(0.0396)y + 9.5442(0.0158)z = 8.2239(0.0250)
Atoms
Dist. (10 A)
C22
4.3
N5
3.9
C20
4.3
N6
4.7
C21
629.1
P2
643.9
3
˚

Synthesis and crystal structure of title compound
451
Fig. 2. Molecular Packing of the 2-Propyl-5-phenyl-1,4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino
[1,2-a][1,3,2]benzodiazaphosphorine 3-Oxide.
The EI-MS spectrum of the compound
displayed the molecular ion peak and all the
fragmentation products were consistent with
its structure. The IR spectrum showed normal
stretching absorption bands, indicating the exis-
Acknowledgments
This work was supported by the National Natural
Science Foundation of China and Foundation for
University Key Teacher by the Ministry of Education.
1
tence of the groups P O (1346.2 cm ), P N
1
(1034.0 cm ), and the two amide carbonyls
References
1
(1669.1 and 1643.4 cm ). The satisfactory el-
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