New phosphoric triamides: Chlorine substituens effects and polymorphism

Article abstract of DOI:10.1002/hc.20592

New phosphoric triamides 1 - 10 were synthesized by the reaction of N-2,4-dichlorobenzoyl phosphoramidic dichloride with various cyclic aliphatic amines, and the products were characterized by ¹H, ¹³C, ³¹P NMR, and IR spec

Full text of DOI:10.1002/hc.20592

Heteroatom Chemistry
Volume 21, Number 3, 2010
New Phosphoric Triamides: Chlorine
Substituents Effects and Polymorphism
Khodayar Gholivand,1 Nasrin Oroujzadeh,1 and Zahra Shariatinia2
1Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
2Department of Chemistry, Amirkabir University of Technology, P.O. Box 159163-4311,
Tehran, Iran
Received 22 November 2009; revised 18 February 2010
INTRODUCTION
ABSTRACT: New phosphoric triamides 1−10 were
synthesized by the reaction of N-2,4-dichlorobenzoyl
phosphoramidic dichloride with various cyclic
aliphatic amines, and the products were characterized
by 1H, 13C, 31P NMR, and IR spectroscopy and elemen-
tal analysis. Surprisingly, the 1H NMR spectra of com-
pounds 1−7 demonstrate long-range 4 J(H,H) cou-
pling constant from 1.5 to 1.9 Hz. Comparison of the
NMR and IR spectra of N-benzoyl, N-4-chlorobenzoyl,
and N-2,4-dichlorobenzoyl phosphoric triamide ana-
logues indicates that N-2,4-dichlorobenzoyl deriva-
tives have the most upfield δ(31P) and the highest
ν(C O) values. The crystal structures of 3, 4, 6, 6a,
and 10 have been determined by X-ray crystallogra-
phy. Interestingly, the structures of 6 and 6a are poly-
morphic. All structures form dimers through strong,
intermolecular P O· · ·H N hydrogen bonds. The
dimers connect to each other via weak C H· · ·Cl and
C H· · ·OH bonds to produce two-dimensional poly-
meric chains for 4 and three-dimensional networks for
others. Among new synthesized N-2,4-dichlorobenzoyl
phosphoric triamides, one indicated polymorphism.
All structures were characterized by 1H, 13C, 31P
NMR, and infrared spectroscopy and elemental anal-
The increasing interests in research on phospho-
ramidates chemistry in the present years are due
to the valuable applications of these derivatives as
prodrugs [1–3], insecticides and pesticides [4–7], ef-
ficient ligands in coordination chemistry [8–11], the-
oretical chemistry [12,13], synthesis [14–17], and
structural study [18–22]. So far, the substituent ef-
fects on the structural parameters have been dis-
cussed to some extent [23–25]. The crystal structures
of several phosphoramidates have already been de-
termined by X-ray crystallography [18–29]. Forma-
tion of polymorphs is important not only because
of their structural differences but also because of
their various therapeutical properties [30]. In recent
years, polymorphism has found important applica-
tions in the areas of pigments, explosives, electron-
ics, food, agrochemical, and, above all, pharmaceuti-
cal industry in which regulatory controls necessitate
the close examination of all products under devel-
opment for their solid-state behavior [31]. Barendt
et al. [32] reported two polymorphs of diazaphos-
——————–
|
|
phorus compound C6H5P(O)[NHC6H4NH].
Herein, following on our previous stud-
ies, we represent the synthesis, spectroscopic,
and structural investigations of 10 new N-2,4-
dichorobenzoyl phosphoric triamides. Also, we
were surprised to obtain two polymorphs of
compound 2,4-Cl2C6H3C(O)NHP(O)(NC4H8O)2. In
addition, the spectroscopic results of these com-
pounds have been compared with those of their N-
benzoyl and N-4-chlorobenzoyl phosphoric triamide
analogues.
ꢀ
C
ysis.
2010 Wiley Periodicals, Inc. Heteroatom Chem
21:168–180, 2010; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.20592
Correspondence to: Khodayar Gholivand; e-mail: gholi kh@
modares.ac.ir.
Contract grant sponsor: Research Council of Tarbiat Modares
University, Tehran, Iran.
c
ꢀ
2010 Wiley Periodicals, Inc.
168

New Phosphoric Triamides 169
129.85 (d, 3 J(P,C) = 10.7 Hz), 130.83 (s), 131.91 (s),
EXPERIMENTAL
132.53 (s), 139.44 (s), 164.30 (s, C O).
X-ray Measurements
X-ray data of compounds 3, 4, 6, and 10 were col-
lected by using a Bruker SMART 1000 CCD [33a]
and of 6a by using a Bruker APEX II CCD area detec-
tor [33b] single-crystal diffractometer with graphite
General Procedure for the Synthesis of Com-
pounds 2–9. To a solution of 1 mmol of N-2,4-
dichlorobenzoyl phosphoramidic dichloride (1) in
dry acetonitrile at −5◦C, 4 mmol of correspond-
ing amine was added dropwise and the mixture
was stirred for 6 h. After evaporating the sol-
vent, the residue was washed with distilled wa-
ter and acetonitrile and then recrystallized in a
methanol/chloroform solution.
˚
monochromated MoKα radiation (λ = 0.71073 A).
The structures were refined with SHELXL-97 [33–
35] by full-matrix least-squares on F2. The positions
of hydrogen atoms were obtained from the differ-
ence Fourier map. Routine Lorentz and polarization
corrections were applied, and an absorption correc-
tion was performed using the SADABS program for
these structures [35a,b].
N-2,4-Dichlorobenzoyl-Nꢁ,Nꢁꢁ -bis(pyrrolidinyl)
Phosphoric Triamide (2). Yield: 88%. Decomposed
at 238.9◦C. Anal. Calcd. for C15H20Cl2N3O2P (%): C,
47.89; H, 5.36; N, 11.17. Found: C, 47.90; H, 5.35; N,
11.17. IR (KBr, cm−1): νmax = 3045 (s, NH), 2855 (s,
CH2), 1681 (s, C O), 1576 (m), 1467 (s), 1281 (m),
1245 (s), 1209 (s, P O), 1179 (s), 1121 (s), 1089 (s),
1045 (m), 1010 (m), 866 (m), 808 (m), 773 (m), 675
(m), 575 (s), 531 (m), 510 (m), 439 (m). 31P NMR
(202.46 MHz; d6-DMSO; 85% H3PO4): δ 6.72 (m).
1H NMR (500.13 MHz; d6-DMSO; Me4Si): δ 1.78 (m,
8H, CH2), 3.16 (m, 8H, CH2), 7.47 (m, 2H, Ar H),
Spectroscopic Measurements
1H, 13C, and 31P spectra were recorded on a
Avance DRS 500 spectrometer (Bruker Karlosuhe,
1
Germany). H and 13C chemical shifts were deter-
mined relative to internal Me4Si and 31P chemical
shifts were determined relative to 85% H3PO4 as ex-
ternal standards, respectively. The strong field acqui-
1
sition of H, 13C, and 31P NMR spectra was 500.13,
125.77, and 202.46 MHz, respectively. Infrared (IR)
spectra were recorded on a Shimadzu model IR-60
spectrometer (Shimadzu, Kyoto, Japan). Elemental
analysis was performed on a CHN-O-RAPID appa-
ratus (Heraeus, Hanau, Germany). Melting points
were determined on an Electrothermal instrument
(Electrthermal, Essex, UK).
4
7.66 (d, J(H,H) = 1.5 Hz, 1H, Ar H), 9.38 (s, 1H,
NH). 13C NMR (125.75 MHz; d6-DMSO; Me4Si): δ
3
2
25.81 (d, J(P,C) = 7.9 Hz, CH2), 45.81 (d, J(P,C)
= 4.0 Hz, CH2), 127.16 (s), 128.89 (s), 130.00 (s),
3
130.67 (s), 134.60 (s), 135.59 (d, J(P,C) = 8.1 Hz),
167.19 (s, C O).
N-2,4-Dichlorobenzoyl-Nꢁ,Nꢁꢁ -bis(piperidinyl)
Synthesis
Phosphoric Triamide (3). Yield: 90%, m.p.
=
N-2,4-Dichlorobenzoyl Phosphoramidic Dichlo-
ride (1). A 1:1 molar ratio of phosphorus pentachlo-
ride and 2,4-dichlorobenzamide was refluxed in CCl4
for 8 h and then the resulting solution was cooled to
room temperature. Formic acid was syringed drop-
wise into the stirring solution for 20 min and stirred
for 6 h to yield a white precipitate that was filtered
and dried in vacuum.
229.4◦C. Anal. Calcd. for C17H24Cl2N3O2P (%): C,
50.51; H, 5.98; N, 10.39. Found: C, 50.50; H, 5.98;
N, 10.38. IR (KBr, cm−1): νmax = 3035 (s, NH),
2910 (s, CH2), 1679 (s, C O), 1576 (m), 1466
(s), 1444 (s), 1232 (m), 1208 (s, P O), 1186 (s),
1163 (m), 1102 (m), 1071 (s), 955 (s), 849 (m),
805 (m), 773 (m), 720 (m), 575 (s), 439 (m). 31P NMR
(202.46 MHz; d6-DMSO; 85% H3PO4): δ 8.67 (m). 1H
NMR (500.13 MHz; d6-DMSO; Me4Si): δ 1.45 (m, 8H,
CH2), 1.51 (m, 4H, CH2), 3.04 (m, 8H, CH2), 7.41–
Yield: 71%, m.p. = 120.4◦C. Anal. Calcd. for
C7H4Cl4NO2P (%): C, 27.40; H, 1.31; N, 4.56. Found:
C, 27.39; H, 1.31; N, 4.55. IR (KBr, cm−1): νmax
=
7.48 (m, 2H, Ar H), 7.66 (d, J(H,H) = 1.6 Hz, 1H,
4
3100 (s), 2850 (w), 1707 (vs, C O), 1582 (s), 1428
(vs), 1403(s), 1276 (s), 1249 (s), 1227 (vs, P O),
1142 (w), 1102 (vs), 1043 (m), 896 (s), 866 (w),
832 (m), 781 (m), 756 (m), 678 (m), 586 (m), 516
(m). 31P NMR (202.46 MHz; CDCl3; 85% H3PO4): δ
Ar H), 9.29 (s, 1H, NH). 13C NMR (125.75 MHz; d6-
3
DMSO; Me4Si): δ 24.12 (s), 25.68 (d, J(P,C) = 5.0
Hz, CH2), 44.88 (d, 2 J(P,C) = 2.0 Hz, CH2), 127.17 (s),
128.97 (s), 129.93 (s), 130.66 (s), 134.57 (s), 135.66
(s), 167.17 (s, C O).
1
5.99 (m). H NMR (500.13 MHz; CDCl3; Me4Si): δ
3
4
7.40 (dd, J(H,H) = 8.3 Hz, J(H,H) = 1.9 Hz, 1H,
N-2,4-Dichlorobenzoyl-Nꢁ,Nꢁꢁ-bis(hexamethylenyl)
Phosphoric Triamide (4). Yield: 85%, m.p. = 181.8◦
C. Anal. Calcd. for C19H28Cl2N3O2P (%): C, 52.79; H,
6.53; N, 9.72. Found: C, 52.77; H, 6.52; N, 9.71. IR
Ar H), 7.51 (d, J(H,H) = 1.9 Hz, 1Ha, Ar H), 7.75
4
3
(d, J(H,H) = 8.3 Hz, 1H, Ar H), 9.23 (s, 1H, NH).
13C NMR (125.75 MHz; CDCl3; Me4Si): δ 127.95 (s),
Heteroatom Chemistry DOI 10.1002/hc

170 Gholivand, Oroujzadeh, and Shariatinia
3
(KBr, cm−1): νmax = 3425 (w, NH), 3050 (m, CH2),
2900 (s, CH2), 1674 (s, C O), 1575 (m), 1435 (s),
1380 (m), 1283 (m), 1228 (m), 1186 (s, P O), 1150
(m), 1089 (m), 1057 (s), 940 (m), 895 (m), 871 (m),
772 (m), 750 (m), 700 (m), 571 (w), 439 (m). 31P
NMR (202.46 MHz; d6-DMSO; 85% H3PO4): δ 12.41
(m). 1H NMR (500.13 MHz; d6-DMSO; Me4Si): δ 1.60
66.34 (d, J(P,C) = 5.6 Hz, CH2), 127.23 (s), 129.04
(s), 130.72 (s), 134.87 (s), 135.23 (d, 3 J(P,C) = 9.3
Hz), 167.44 (s, C O).
N - 2,4 - Dichlorobenzoyl - Nꢁ,Nꢁꢁ - bis(cyclopropyl)
Phosphoric Triamide (7). Yield: 73%, m.p.
=
164.8◦C. Anal. Calcd. for C13H16Cl2N3O2P (%): C,
44.85; H, 4.63; N, 12.07. Found: C, 44.84; H, 4.63;
N, 12.06. IR (KBr, cm−1): νmax = 3265 (s, NH), 3100
(m, CH), 2910 (w), 1656 (s, C O), 1585 (m), 1438 (s),
1355 (s), 1274 (m), 1240 (m), 1201 (s, P O), 1169 (w),
1133 (m), 1100 (m), 1045 (m), 1023 (m), 969 (m), 891
(s), 865 (m), 833 (m), 772 (s), 709 (w), 689 (m), 621
(w), 570 (m), 508 (m), 430 (m). 31P NMR (202.46
3
(m, 16H, CH2), 3.14 (m, 8H, CH2), 7.41 (d, J(H,H)
= 8.2 Hz, 1H, Ar H), 7.49 (dd, 3 J(H,H) = 8.2 Hz,
4 J(H,H) = 1.9 Hz, 1H, Ar H), 7.66 (d, 4 J(H,H) = 1.9
Hz, 1H, Ar H), 9.32 (s, 1H, NH). 13C NMR (125.75
MHz; d6-DMSO; Me4Si): δ 26.28 (s, CH2), 29.71 (d,
2
3 J(P,C) = 3.9 Hz, CH2), 46.92 (d, J(P,C) = 4.5 Hz,
CH2), 127.19 (s), 129.02 (s), 129.89 (s), 130.69 (s),
3
134.59 (s), 135.66 (d, J(P,C) = 9.3 Hz), 167.10 (s,
1
MHz; d6-DMSO; 85% H3PO4): δ 6.54 (m). H NMR
C O).
(500.13 MHz; d6-DMSO; Me4Si): δ 0.43–0.54 (m, 8H,
CH2), 2.30 (m, 2H), 4.74 (d, 2 J(PNH) = 11.7 Hz, 2H,
N-2,4-Dichlorobenzoyl-Nꢁ,Nꢁꢁ-bis(4-methyl pipe-
ridinyl) Phosphoric Triamide (5). Yield: 80%, m.p.
= 184.5◦C. Anal. Calcd. for C19H28Cl2N3O2P (%): C,
52.79; H, 6.53; N, 9.72. Found: C, 52.78; H, 6.53;
N, 9.71. IR (KBr, cm−1): νmax = 3475 (w, NH), 3095
(m), 2920 (s, CH), 1693 (s, C O), 1580 (m), 1440 (vs,
C C), 1375 (m), 1343 (w), 1280 (m), 1249 (m), 1195
(s, P O), 1160 (m), 1116 (m), 1063 (s), 959 (m), 939
(s), 868 (m), 810 (m), 777 (m), 753 (m), 508 (m), 449
(m). 31P NMR (202.46 MHz; d6-DMSO; 85% H3PO4):
δ 8.72 (m). 1H NMR (500.13 MHz; d6-DMSO; Me4Si):
δ 0.88 (d, 3 J(H,H) = 6.5 Hz, 6H, CH3), 1.04 (m,
4
NHamine), 7.44–7.49 (m, 2H, Ar H), 7.65 (d, J(H,H)
= 1.6 Hz, 1H, Ar H), 9.47 (d, 2 J(PNH) = 7.0 Hz, 1H,
NHamide). 13C NMR (125.75 MHz; d6-DMSO; Me4Si):
3
δ 6.15 (d, J(P,C) = 6.3 Hz, CH2), 6.25 (d, 3 J(P,C) =
5.1 Hz, CH2), 22.12 (s, CH), 127.12 (s), 129.06 (s),
3
130.17 (s), 130.84 (s), 134.64 (s), 135.36 (d, J(P,C)
= 8.5 Hz), 167.03 (s, C O).
N - 2,4 - Dichlorobenzoyl - Nꢁ,Nꢁꢁ - bis(cyclopentyl)
Phosphoric Triamide (8). Yield: 75%, m.p.
=
222.2◦C. Anal. Calcd. for C17H24Cl2N3O2P (%): C,
50.51; H, 5.98; N, 10.39. Found: C, 50.49; H, 5.98;
N, 10.40. IR (KBr, cm−1): νmax = 3370 (s, NH), 3060
(s), 3000 (s), 2870 (s), 1659 (s, C O), 1582 (m), 1552
(w), 1474 (s), 1437 (s, C C), 1372 (w), 1287 (m),
1208 (vs, P O), 1176 (m), 1106 (m), 1049 (m), 947
(m), 912 (m), 876 (m), 844 (m), 811 (m), 769 (m),
700 (w), 568 (w), 511 (m). 31P NMR (202.46 MHz;
d6-DMSO; 85% H3PO4): δ 5.25 (m). 1H NMR (500.13
MHz; d6-DMSO; Me4Si): δ 1.42 (m, 8H), 1.60 (m, 4H),
1.75 (m, 4H), 3.47 (m, 2H), 4.25 (dd, 2 J(PNH) = 9.3
Hz, 3 J(H,H) = 8.8 Hz, 2H, NHamine), 7.43 (d, 3 J(H,H)
= 8.3 Hz, 1H, Ar H), 7.47 (d, 3 J(H,H) = 8.5 Hz,
1H, Ar H), 7.62 (s, 1H, Ar H), 9.46 (s, 1H, NHamide).
13C NMR (125.75 MHz; d6-DMSO; Me4Si): δ 22.79
2
4H), 1.44 (m, 2H), 1.55 (d, J(H,H) = 12.1 Hz, 4H),
2.59–2.66 (m, 4H), 3.48 (m, 4H), 7.41 (d, 3 J(H,H)
= 8.2 Hz, 1H, Ar H), 7.47 (dd, 3 J(H,H) = 8.2 Hz,
4 J(H,H) = 1.9 Hz, 1H, Ar H), 7.66 (d, 4 J(H,H) =
1.9 Hz, 1H, Ar H), 9.40 (2 J(PNH) = 7.5 Hz, 1H,
NHamide). 13C NMR (125.75 MHz; d6-DMSO; Me4Si):
3
δ 22.02 (s, CH3), 30.44 (s, CH), 34.03 (d, J(P,C) =
5.0 Hz, CH2), 34.13 (d, 3 J(P,C) = 5.0 Hz, CH2), 42.20
2
2
(d, J(P,C) = 2.3 Hz, CH2), 44.38 (d, J(P,C) = 2.6
Hz, CH2), 127.21 (s), 129.01 (s), 130.68 (s), 134.62
(s), 135.62 (d, 3 J(P,C) = 8.9 Hz), 167.17 (s, C O).
N - 2,4 - Dichlorobenzoyl - Nꢁ,Nꢁꢁ - bis(morpholinyl)
Phosphoric Triamide (6). Yield: 83%, m.p.
=
238.0◦C. Anal. Calcd. for C15H20Cl2N3O4P (%): C,
44.13; H, 4.94; N, 10.29. Found: C, 44.12; H, 4.95; N,
10.30. IR (KBr, cm−1): νmax = 3410 (m, NH), 3040 (m,
CH2), 2850 (m, CH2), 1673 (s, C O), 1576 (m), 1452
(s), 1371 (m), 1286 (m), 1254 (m), 1187 (s, P O),
1110 (s), 1087 (m), 967 (s), 910 (m), 866 (m), 823
(m), 744 (m). 31P NMR (202.46 MHz; d6-DMSO; 85%
H3PO4): δ 8.90 (m). 1H NMR (500.13 MHz; d6-DMSO;
3
(s, CH2), 22.90 (s, CH2), 34.02 (d, J(P,C) = 5.0 Hz,
CH2), 34.23 (d, 3 J(P,C) = 6.4 Hz, CH2), 51.92 (s, CH),
127.13 (s), 129.11 (s), 130.19 (s), 130.91 (s), 134.66
(s), 135.26 (d, 3 J(P,C) = 8.6 Hz), 166.89 (s, C O).
N - 2, 4 - Dichlorobenzoyl - Nꢁ, Nꢁꢁ - bis(cyclohexyl)
Phosphoric Triamide (9). Yield: 82%, m.p.
=
3
Me4Si): δ 3.09 (m, 8H, CH2), 3.55 (t, J(H,H) = 4.5
215.5◦C. Anal. Calcd. for C19H28Cl2N3O2P (%): C,
52.79; H, 6.53; N, 9.72. Found: C, 52.78; H, 6.53;
N, 9.72. IR (KBr, cm−1): νmax = 3415 (m, NH), 3240
(s, NH), 2905 (s, CH2), 1649 (s, C O), 1579 (m),
4
Hz, 8H, CH2), 7.49 (m, 2H, Ar H), 7.68 (d, J(H,H)
= 1.6 Hz, 1H, Ar H), 9.65 (s, 1H, NH). 13C NMR
(125.75 MHz; d6-DMSO; Me4Si): δ 44.31 (s, CH2),
Heteroatom Chemistry DOI 10.1002/hc

New Phosphoric Triamides 171
Cl
O
Cl
O
O
P
HCOOH
NH2
N
Cl
PCl5
+
H
Cl
Cl
Cl
1
Cl
O
O
P
Cl
O
O
P
Cl
O
O
P
CH3
N
N
N
N
N
N
H
H
H
N
N
N
CH3
Cl
Cl
Cl
10
2
3
Cl
O
O
P
N
N
H
Cl
O
O
N
P
Cl
N
N
H
H
Cl
O
O
HN
4
P
Cl
N
Cl
H
Cl
9
Cl
Cl
O
O
1
P
N
N
Cl
O
O
H
N
CH3
P
Cl
N
N
H
H
HN
Cl
H3C
5
8
Cl
O
O
P
Cl
O
O
P
N
H
N
H
N
N
HN
H
O
N
Cl
Cl
O
6
7
SCHEME 1 The preparation pathway for the synthesis of compounds 1–10.
1432 (s), 1277 (m), 1235 (m), 1201 (m, P O), 1125
(m), 1094 (s), 917 (m), 879 (m), 766 (m). 31P NMR
(202.46 MHz; d6-DMSO; 85% H3PO4): δ 5.59 (m).
1H NMR (500.13 MHz; d6-DMSO; Me4Si): δ 1.16–
2.10 (m, 20H), 2.94 (s, 2H), 4.16 (s, 2H, NHamine),
7.49 (m, 3H, Ar H), 8.85 (b, 1H, NHamide). 13C NMR
(125.75 MHz; d6-DMSO; Me4Si): δ 24.74 (s), 25.09 (s),
34.95 (s), 35.34 (s), 49.21 (s), 127.19 (s), 129.08 (s),
130.02 (s), 130.76 (s), 134.57 (s), 135.40 (s), 166.91
(s, C O).
N-2,4-Dichlorobenzoyl-Nꢁ,Nꢁꢁ -bis(N-methylcyclo-
hexyl) Phosphoric Triamide (10). To a solution of
1 mmol of N-2,4-dichlorobenzoyl phosphoramidic
dichloride (1) in dry chloroform at −5◦C, a mixture
of N-methylcyclohexylamine (2 mmol) and triethy-
lamine (2 mmol) was added dropwise and stirred
for 4 h. After evaporating the solvent, the residue
was washed with distilled water and acetonitrile
and then recrystallized in a methanol/chloroform
solution.
Heteroatom Chemistry DOI 10.1002/hc

172 Gholivand, Oroujzadeh, and Shariatinia
TABLE 1 Some Spectroscopic Data of Compounds 1–10 and Their Analogues
2J(P,C)- 3J(P,C)- 3J(P,C)-
δ(31P) 2J(PNH) 4J(H,H) aliphatic aliphatic aromatic ν(P O) ν(C O)
Compound
(ppm)
(Hz)
(Hz)
(Hz)
(Hz)
(Hz) (cm−1) (cm−1) Ref.
a,b
2,4-Cl2-C6H3-C(O)NHP(O)Cl2 (1)
5.99
6.72
8.67
–
–
–
–
1.9
1.5
1.6
1.9
1.9
–
—
10.7
8.1
–
9.3
8.9
1227 1707
1209 1681
1208 1679
1186 1674
1195 1693
a,b
a,b
a,b
a,b
2,4-Cl2-C6H3-C(O)NHP(O)(NC4H8)2 (2)
2,4-Cl2-C6H3-C(O)NHP(O)(NC5H10)2 (3)
2,4-Cl2-C6H3-C(O)NHP(O)(NC6H12)2 (4)
4.0
2.0
4.5
7.9
5.0
3.9
12.41
2,4-Cl2-C6H3-C(O)NHP(O)(4-CH3-NC5H9)2 8.72 7.5 (amide)
2.3, 2.6 5.0, 5.0
(5)
a,b
a,b
2,4-Cl2-C6H3-C(O)NHP(O)(NC4H8O)2 (6)
2,4-Cl2-C6H3-C(O)NHP(O)(NHC3H5)2 (7)
8.90
–
1.6
–
–
5.6
5.1, 6.3
9.3
8.5
1187 1673
1201 1656
6.54 11.7 (amine) 1.6
7.0 (amide)
5.25 9.3 (amine)
a,b
a,b
a,b
2,4-Cl2-C6H3-C(O)NHP(O)(NHC5H9)2 (8)
2,4-Cl2-C6H3-C(O)NHP(O)(NHC6H11)2 (9)
2,4-Cl2-C6H3-C(O)NHP(O)[N(CH3)(C6H11)]2 11.96
–
–
–
–
–
3.1
5.0, 6.4
8.6
–
–
1208 1659
1201 1649
1178 1682
5.59
–
–
–
–
(10)
4-Cl-C6H4-C(O)NHP(O)Cl2 (11)
4-Cl-C6H4-C(O)NHP(O)(NC5H10)2 (12)
10.52 12.0 (amide)
11.64 3.2 (amide)
–
–
5.4 (C O)
–
5.9
9.8
7.3
1226 1683 26c
1207 1667 26c
2.8
1.9 (C O)
4-Cl-C6H4-C(O)NHP(O)(NC4H8O)2 (13)
10.87 5.5 (amide)
–
4.5
1.1
6.3
1193 1666 29c
1.9 (C O)
4-Cl-C6H4-C(O)NHP(O)(NC6H12)2 (14)
4-Cl-C H -C(O)NHP(O)(NHC H5) (15)
4-Cl-C6H4-C(O)NHP(O)(NHC35H )2 (16)
14.42
–
–
–
–
–
4.7
–
–
6.3
2.9
8.5
–
7.8
5.3
1178 1660 28
1205 1642 28c
1218 1621 27c
1215 1635 26c
10.56 5.0 (amide)
8.86 5.1 (amide)
6.21 4.1 (amide)
5.8, 5.1
7.0, 4.7
10.1, 3.8
4-Cl-C66H44-C(O)NHP(O)(NHC6H9 2) (17)
11 2
1.8 (C O)
5.5
C H5-C(O)NHP(O)(NC H ) (18)
6
8.84
12.02
–
–
–
–
8.6
4.7
8.7
8.5
1202 1665 42c
1203 1667 41c
C6H5-C(O)NHP(O)(NC54H1802)2 (19)
4.7
3.9 (C O)
4.7
2.9, 0.0 4.9, 5.1
C H5-C(O)NHP(O)(NC6H12)2 (20)
C6H5-C(O)NHP(O)(4-CH -NC5H ) (21)
C6H5-C(O)NHP(O)(NHC 3H5) (292)2
C6H5-C(O)NHP(O)(NHC35H )2(23)
C6H5-C(O)NHP(O)(NHC H1912)2 (24)
14.70 3.8 (amide)
–
–
–
–
–
4.2
8.7
8.5
–
8.1
6.5
1182 1660 43c
1190 1668 41c
1202 1635 28c
1204 1637 27c
1205 1630 26c
12.13
8.80
8.99
–
–
–
–
–
6.4
5.9, 4.9
4.8, 6.2
3.9
7.85 5.5 (amide)
6
6
3.4 (C O)
5.2, 4.8 3.1, 3.9
2.9 (C O)
C6H5-C(O)NHP(O)[N(CH3)(C6H11)]2 (25)
13.56 5.9 (amide)
–
8.6
1183 1670 44b
aThis work.
bNMR solvent is d6-DMSO.
cNMR solvent is CDCl3.
Yield: 78%, m.p. = 180.3◦C. Anal. Calcd. for
C21H32Cl2N3O2P (%): C, 54.79; H, 7.01; N, 9.13.
Found: C, 54.78; H, 7.00; N, 9.12. IR (KBr, cm−1): νmax
= 3050 (m, CH2), 2905 (s, CH2), 1682 (s, C O), 1575
(m), 1460 (s), 1431 (s), 1383 (m), 1268 (m), 1221 (m),
1178 (s, P O), 1154 (m), 1099 (m), 1044 (m), 1000
(s), 974 (s), 849 (s), 809 (m), 770 (m), 747 (m), 571
(m), 538 (m), 503 (m). 31P NMR (202.46 MHz; d6-
20.23 (s), 30.34 (s), 54.08 (s), 127.20 (s), 128.28 (s),
129.82 (s), 130.66 (s), 134.54 (s), 135.77 (s), 167.01
(s, C O).
RESULTS AND DISCUSSION
Spectroscopic Study
From
the
reaction
of
PCl5
with
2,4-
1
DMSO; 85% H3PO4): δ 11.96 (m). H NMR (500.13
MHz; d6-DMSO; Me4Si): δ 1.03 (s, 3H, N-CH3), 1.22
dichlorobenzamide and then oxidation with formic
acid, compound N-2,4-Cl2C6H3C(O)NHP(O)Cl2 (1)
was obtained as a new intermediate that interacted
with various amines to yield several new phosphoric
triamides 2–10 (Scheme 1). Spectroscopic data
of these compounds and their analogues N-4-
ClC6H4C(O)NHP(O)X2 and C6H5C(O)NHP(O)X2,
(s, 3H, N-CH3), 1.48–1.72 (m, 16H), 3.28 (s, 6H), 7.38
3
3
(d, J(H,H) = 6.6 Hz, 1H, Ar H), 7.47 (d, J(H,H)
= 6.6 Hz, 1H, Ar H), 7.66 (s, 1H, Ar H), 9.31 (s,
1H, NH). 13C NMR (125.75 MHz; d6-DMSO; Me4Si):
δ 25.06 (s), 25.63 (s), 27.27 (d, 2 J(P,C) = 3.1 Hz),
Heteroatom Chemistry DOI 10.1002/hc

New Phosphoric Triamides 173
TABLE 2 Crystallographic Data for Compounds 3, 4, and 10
3
4
10
Empirical formula
Formula weight
Temperature (K)
C17H24Cl2N3O2P
404.26
120(2)
C19H28Cl2N3O2P
432.31
120(2)
C21H32Cl2N3O2P
460.37
120(2)
˚
Wavelength (A)
0.71073
0.71073
0.71073
Crystal system, space group
Unit cell dimensions
Triclinic, P-1
Orthorhombic, Pbca
Monoclinic, P21/c
˚
a (A)
9.9189(6)
10.1898(7)
11.0809(7)
103.9600(10)
116.3000(10)
92.3010(10)
960.36(11)
2, 1.398
18.5102(7)
10.4647(6)
21.4451(11)
90
90
90
4154.0(4)
8, 1.383
0.409
1824
10.463(2)
21.076(4)
10.4944(19)
90
102.139(6)
90
2262.5(7)
4, 1.352
0.380
976
˚
b (A)
˚
c (A)
α (◦)
β (◦)
γ (◦)
3
˚
V (A )
Z, calculated density (Mg m−3
)
Absorption coefficient (mm−1
F(000)
)
0.437
424
Crystal size (mm)
0.55 × 0.40 × 0.30
2.09–28.00
−13 ≤ h ≤ 13
−13 ≤ k ≤ 13
−14 ≤l ≤ 14
9,926/4,609 [R(int) =
0.0188]
0.30 × 0.20 × 0.15
1.90–29.99
−25 ≤ h ≤ 26
−14 ≤ k ≤ 14
−30 ≤ l ≤ 30
45,607/6,037 [R(int) =
0.0746]
0.30 × 0.10 × 0.08
1.93–26.00
−12 ≤ h ≤ 8
−25 ≤ k ≤ 25
−12 ≤ l ≤ 12
10,668/4,405 [R(int) =
0.0347]
θ range for data collection (◦)
Limiting indices
Reflections collected/unique
Completeness to θ
Absorption correction
99.4%
99.6%
99.2%
Semiempirical from
equivalents
0.858 and 0.847
Full-matrix
Semiempirical from
equivalents
0.943 and 0.884
Full-matrix
Semiempirical from
equivalents
0.968 and 0.957
Full-matrix
Max. and min. transmission
Refinement method
least-squares on F2
4609/0/230
1.012
least-squares on F2
6037/0/244
1.009
least-squares on F2
4405/1/268
1.003
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
R1 = 0.0330, wR2 =
R1 = 0.0574, wR2 =
R1 = 0.0627, wR2 =
0.0858
0.1280
0.1196
R indices (all data)
R1 = 0.0361, wR2 =
0.0886
0.382 and −0.457
R1 = 0.0789, wR2 =
0.1375
0.675 and −0.385
R1 = 0.0931, wR2 =
0.1301
0.531 and −0.837
−3
˚
Largest diff. peak and hole (e A
)
where X = amine, have been summarized in Table 1.
31P NMR spectra indicate that δ(31P) shifts to down
fields with increasing ring sizes of amine groups
from five to seven members in molecules 2–4.
Similar results were obtained for their analogues 12
and 14. In both sets of compounds 2–4 (with N atom
as a ring member) and 7–10 (with N atom out of the
ring) for molecules with the biggest amine group
(4 and 10), δ(31P) is the most downfield. Results
show that among compounds 1–25, the N-2,4-
dichlorobenzoyl derivatives have the most upfield
δ(31P) in comparison with their N-4-chlorobenzoyl
and N-enzoyl analogues.
solvent, certain impurities or additives, concentra-
tion, temperature, the geometry of covalent bonds,
and the stirring conditions [36,37], affect the forma-
tion of a polymorph. Here, SnCl2(CH3)2 acts as an
additive and helps in the formation of polymorph
6a. The NMR and IR spectra of 6 and 6a do not
indicate remarkable differences and are nearly the
same.
1
Interestingly, the H NMR spectra of molecules
1–7 display long-range 4 J(H,H) coupling con-
stants (range = 1.5–1.9 Hz) for the coupling of aro-
matic protons in 2,4-dichlorophenyl rings. Typi-
cally, 4 J(H,H) coupling constants for the phenyl
rings are in the range of 1 to 3 Hz and the
particular values seem to depend as much on
the pattern of substitution as the nature of the
substituent [38]. This coupling was not observed
It is noteworthy that the reaction of com-
pound 6 with SnCl2(CH3)2 in 2:1 molar ratio in a
methanol/chloroform mixture gave its polymorph
6a. It must be noted that several parameters such as
Heteroatom Chemistry DOI 10.1002/hc

174 Gholivand, Oroujzadeh, and Shariatinia
TABLE 3 Crystallographic Data for Compounds 6 and 6a
6
6a
Empirical formula
Formula weight
Temperature (K)
C15H20Cl2N3O4P
408.21
120(2)
C15H20Cl2N3O4P
408.21
100(2)
˚
Wavelength (A)
0.71073
0.71073
Crystal system, space group
Unit cell dimensions
Monoclinic, P21/n
Triclinic, P-1
˚
a (A)
9.3320(6)
10.2359(7)
19.0063(13)
90
91.132(2)
90
1815.2(2)
4, 1.494
0.472
848
9.7293(6)
10.2201(7)
10.9196(7)
105.599(1)
103.461(1)
110.791(1)
910.42(10)
2, 1.489
0.470
424
˚
b (A)
˚
c (A)
α (◦)
β (◦)
γ (◦)
3
˚
V (A )
Z, Calculated density (Mg m−3
)
Absorption coefficient (mm−1
F(000)
)
Crystal size (mm)
0.35 × 0.25 × 0.20
0.45 × 0.37 × 0.20
θ range for data collection (◦)
Limiting indices
2.14 to 29.00
2.08 to 25.99
−12 ≤ h ≤ 12,
−11 ≤h ≤ 11,
−13 ≤ k ≤ 13,
−12 ≤ k ≤ 12,
−24 ≤ l ≤ 25
−12 ≤ l ≤ 13
Reflections collected/unique
Completeness to θ
19,475/4,785 [R(int) = 0.0598]
6,175/3,537 [R(int) = 0.0171]
99.3%
98.9%
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
Semiempirical from equivalents
0.907 and 0.856
Full-matrix least-squares on F2
4785/0/262
Semiempirical from equivalents
0.912 and 0.816
Full-matrix least-squares on F2
3537/0/230
0.972
1.015
R1 = 0.0505, wR2 = 0.0890
R1 = 0.0369, wR2 = 0.0941
R indices (all data)
Largest diff. peak and hole (e A
R1 = 0.1062, wR2 = 0.1006
R1 = 0.0423, wR2 = 0.0979
−3
˚
)
0.353 and −0.575
1.545 and −0.360
◦
˚
TABLE 4 Selected Bond Lengths (A) and Angles ( ) for Compounds 3, 4, and 10
3
4
10
P(1) O(1)
P(1) N(1)
P(1) N(2)
P(1) N(3)
O(2) C(1)
N(1) C(1)
Cl(1) C(3)
Cl(2) C(5)
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(3) P(1) N(2)
C(1) N(1) P(1)
C(1) N(1) H(1N)
P(1) N(1) H(1N)
1.4858(9)
P(1) O(1)
P(1) N(1)
P(1) N(2)
P(1) N(3)
O(2) C(13)
N(3) C(13)
C(15) Cl(1)
C(17) Cl(2)
1.4795(16)
1.6283(18)
1.6445(18)
1.6908(18)
1.222(2)
1.372(3)
1.735(2)
P(1) O(1)
P(1) N(1)
P(1) N(2)
P(1) N(3)
O(2) C(1)
N(1) C(1)
C(3) Cl(1)
C(5) Cl(2)
1.485(2)
1.693(3)
1.629(3)
1.633(3)
1.212(4)
1.370(4)
1.732(4)
1.738(3)
105.89(14)
110.92(15)
118.35(15)
111.62(15)
105.52(15)
104.50(15)
125.8(2)
119(2)
1.6852(11)
1.6335(11)
1.6322(11)
1.2183(16)
1.3733(16)
1.7365(13)
1.7357(13)
1.734(2)
106.76(5)
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(1) P(1) N(3)
N(2) P(1) N(3)
C(13) N(3) P(1)
C(13) N(3) H(3N)
P(1) N(3) H(3N)
115.10(10)
110.22(10)
106.93(9)
108.06(9)
107.33(9)
109.03(9)
124.47(15)
116.4
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(1) P(1) N(3)
N(2) P(1) N(3)
C(1) N(1) P(1)
C(1) N(1) H(1N)
P(1) N(1) H(1N)
113.62(6)
110.66(5)
106.57(5)
110.53(6)
108.62(6)
126.93(9)
117.6(12)
115.3(12)
118.5
115(2)
Heteroatom Chemistry DOI 10.1002/hc

New Phosphoric Triamides 175
TABLE 6 Selected Torsion Angles (◦) for Compounds 6 and
6a
◦
˚
TABLE 5 Selected Bond Lengths (A) and Angles ( ) for
Compounds 6 and 6a
6
6a
6
6a
O(2) P(1) N(1) C(1)
O(2) P(1) N(2) C(8)
O(2) P(1) N(2) C(11)
O(2) P(1) N(3) C(15)
O(2) P(1) N(3) C(12)
O(1) C(1) C(2) C(7)
O(1) C(1) C(2) C(3)
P(1) N(1) C(1) O(1)
P(1) N(1) C(1) C(2)
P(1) N(2) C(11) C(10)
N(1) P(1) N(2) C(8)
N(1) P(1) N(2) C(11)
N(2) P(1) N(1) C(1)
N(2) P(1) N(3) C(15)
N(3) P(1) N(1) C(1)
N(3) P(1) N(2) C(8)
N(3) P(1) N(2) C(11)
−160.5(2)
−131.5(2)
51.8(2)
−161.34(17)
44.46(18)
−160.73(17)
−94.69(18)
50.09(18)
−53.2(3)
P(1) O(2)
P(1) N(1)
P(1) N(2)
P(1) N(3)
O(1) C(1)
N(1) C(1)
1.479(2)
1.682(2)
1.633(2)
1.631(2)
1.219(3)
1.4820(15)
1.6826(18)
1.6380(17)
1.6340(18)
1.219(3)
1.365(3)
1.480(3)
–
−149.3(3)
20.3(4)
134.3(3)
−42.2(4)
−12.1(4)
166.14(18)
−126.9(2)
−13.1(3)
170.22(19)
76.0(2)
−23.3(3)
−39.7(3)
105.3(2)
−71.4(2)
1.370(4)
125.5(2)
N(3) C(12)
1.554(10)
1.447(10)
107.17(11)
115.12(12)
110.59(12)
106.17(12)
110.87(12)
106.85(11)
126.07(17)
126.7
N(3) C(12ꢁ)
−17.0(3)
164.64(14)
146.77(16)
−73.27(17)
81.53(19)
−41.5(2)
O(2) P(1) N(1)
O(2) P(1) N(2)
O(2) P(1) N(3)
N(2) P(1) N(1)
N(1) P(1) N(3)
N(2) P(1) N(3)
C(1) N(1) P(1)
C(1) N(1) H(1N)
P(1) N(1) H(1N)
106.34(9)
109.85(8)
117.94(9)
111.68(9)
107.00(9)
104.08(9)
127.31(15)
116.1(17)
116.0(17)
143.35(17)
71.77(19)
171.63(15)
−33.56(19)
107.1
for our previously reported phosphoric triamides
[23,26–29].
all the aliphatic carbon atoms of amino moieties
are unequal and indicate different signals. 13C NMR
spectra illustrate the J(P,C O) values between 1.8
2
It is shown in Table 1 that among molecules
1–25, compound 1 has the highest 3 J(P,C)aromatic
,
and 3.9 Hz for some benzoyl and 4-chlorobenzoyl
compounds, whereas this constant was not observed
for their 2,4-dicholorobenzoyl analogues. As the
aliphatic ring size increases from 2 to 4, the ν(P O),
ν(P O) and ν(C O) values. These results are mainly
due to the presence of two electronegative Cl atoms
on the phenyl ring as well as two Cl atoms con-
nected to the phosphorus atom. 13C NMR spectra
of compounds 5, 7, 8, 9, 10, and 21 exhibit that
3
ν(C O), and J(P,C)aliphatic values decrease. It is no-
table that the ν(C O) values are the largest ones in
FIGURE 1 Molecular structure and atom-labeling scheme for compound 3 (50% probability ellipsoids).
Heteroatom Chemistry DOI 10.1002/hc

176 Gholivand, Oroujzadeh, and Shariatinia
Selected bond lengths and angles are presented in
Tables 4 and 5, and molecular structures (ORTEP
view) are shown in Figs. 1–5.
In compound 4, seven-membered aliphatic rings
demonstrate a puckered shape, and in molecules
3, 6, 6a, and 10, the six-membered rings have sta-
ble chair conformation. The interesting point about
structures 6 and 6a is that they are polymorphic. The
polymorph 6a was acquired by adding SnCl2(CH3)2
to a solution of 6. The polymorphs 6 and 6a crystal-
lize in monoclinic and triclinic systems, with Z = 4
and 2, respectively. It could be seen from the ORTEP
figures that disorder in 6 has disappeared in 6a. The
bond lengths and bond angles of these structures are
nearly identical, but their similar torsion angles ex-
hibit great differences (Table 6). Also, there are some
differences in their hydrogen bondings, that is, the
H· · ·A distance in 6 is shorter than that of 6a, exhibit-
ing a stronger H-bond in this compound (Table 7).
In all of these structures, the phosphoryl and
carbonyl groups indicate anticonfigurations and the
phosphorus atoms have distorted tetrahedral con-
figuration. The bond angles around P(1) atoms in
these compounds are in the range from 104.08(9)◦
to 118.35(15)◦.
FIGURE 2 Molecular structure and atom-labeling scheme
for compound 4 (50% probability ellipsoids).
N-2,4-dichlorobenzoyl phosphoramidates relative to
the values of their N-4-chlorobenzoyl and N-benzoyl
analogues, which can be attributed to an increase in
the number of electronegative chlorine atoms on the
phenyl ring.
˚
The P Namide bond lengths (about 1.69 A) are
˚
longer than the P Namine bonds (about 1.63 A) be-
X-ray Crystallography
cause of the resonance interaction of Namide with the
C O π system, which cause a partial multiple bond
character in C Namide (the C Namide bond lengths are
shorter than the C Namine bond lengths; Tables 4 and
5). All of the P N bonds are shorter than the typical
Single crystals of compounds 3, 4, 6, 6a, and 10 were
obtained from a mixture of methanol/chloroform at
room temperature. The crystal data and the details
of the X-ray analysis are given in Tables 2 and 3.
FIGURE 3 Molecular structure and atom-labeling scheme for compound 6 (50% probability ellipsoids).
Heteroatom Chemistry DOI 10.1002/hc

New Phosphoric Triamides 177
FIGURE 4 Molecular structure and atom-labeling scheme for compound 6a (50% probability ellipsoids).
115.56(15)◦, respectively, with average of 118.05◦.
The sum of surrounding angles around N(1), N(2),
and N(3) atoms are 359.96◦, 354.16◦, and 359.37◦,
respectively. Similar results were obtained for the
nitrogen atoms of other structures, which con-
firm the sp2 hybridization of the N atoms, al-
though because of the repulsion and steric in-
teractions, some angles are larger and others
are smaller than 120◦. This observation suggests
the existence of a partial multiple bond between
phosphorus and nitrogen atoms, which has al-
ready been confirmed by the crystallographic data
of our previously reported similar compounds
[22,23,26–29].
˚
P N single bond (1.77 A) [39]. This is probably due
to the electrostatic effects of polar bonds that overlap
with P N sigma bond [40]. The P O bond lengths
in these compounds are larger than the normal P O
˚
bond length (1.45 A) [39].
The environment around the nitrogen atoms is
practically planar. For example, in compound 4,
the angles C(7) N(2) C(12), C(7) N(2) P(1), and
C(12) N(2) P(1) are 114.60(18)◦, 124.00(15)◦, and
These structures contain one amidic hydro-
gen atom and form dimers through intermolecular
P O· · ·H N hydrogen bonds (Table 7), which are
centrosymmetric for all of them except for 6 (ow-
ing to its disorder). Beside these H-bonds, there are
also weak C H· · ·O and C H· · ·Cl hydrogen bonds
in the crystalline network, which produce a two-
dimensional polymeric chain in the crystal lattice of
4 (Fig. 6) and three-dimensional polymers for others
(e.g., see Fig. 7 for 10). There are also π-π stacking
of two phenyl rings, with C C distances in the range
˚
of 3.292 to 3.444 A in these structures. Moreover,
in structure 4, there are intramolecular electrostatic
interactions between O(2) of C O group and ortho
Cl(1) atoms as well as O(2) and N(2) atoms, with
FIGURE 5 Molecular structure and atom-labeling scheme
for compound 10 (50% probability ellipsoids).
Heteroatom Chemistry DOI 10.1002/hc

178 Gholivand, Oroujzadeh, and Shariatinia
FIGURE 6 A two-dimensional polymeric chain produced by strong and weak hydrogen bonds in the crystalline lattice of
compound 4.
˚
˚
bond length becomes shorter. Moreover, compound
19 indicated four conformers in the solid state but
molecules 12 and 3 do not exhibit this feature.
distances equal to 3.030 A and 3.049 A, respectively.
Such an intramolecular electrostatic interaction is
detected between O(2) of C O group and ortho Cl(1)
˚
atoms, with O-Cl distances of about 3.0 A in 3, 6, 6a,
and 10.
SUPPLEMENTARY MATERIAL
A comparison of structure 3 with its analogues
XP(O)(NC5H10)2, where X = 4-ClC6H4C(O)NH (12)
[26], and C6H5C(O)NH (19) [41] indicates that with
an increase in the number of Cl atoms on the ring,
the P O bond becomes longer whereas the C O
Crystallographic data for the structures 3, 4,
6, 6a, and 10 have been deposited with Cam-
bridge Crystallographic Data Center (CCDC)
as supplementary publication numbers: CCDC
FIGURE 7 A two-dimensional polymeric chain produced by strong hydrogen bonds and electrostatic interactions in the
crystalline lattice of compound 10.
Heteroatom Chemistry DOI 10.1002/hc

New Phosphoric Triamides 179
◦
˚
TABLE 7 Hydrogen Bonds for Compounds 3,4, 6, 6a, and 10 (A, )
Compound
(D H· · ·A)
d(D H)
d(H· · ·A)
d(D· · ·A)
DHA
3
4
6
6a
10
N(1) H(1N)· · ·O(1) #1
N(3) H(3N)· · ·O(1) #2
N(1) H(1N)· · ·O(2) #2
N(1) H(1N)· · ·O(2) #3
N(1) H(1N)· · ·O(1) #4
0.86(2)
0.91
0.95
0.82(3)
1.00(2)
1.93(2)
1.89
1.85
1.94(3)
1.831(19)
2.788(2)
2.781(2)
2.795(3)
2.755(3)
2.826(4)
175(1)
167
171
171(2)
176(3)
Symmetry transformations used to generate equivalent atoms: #1, −x + 1, −y + 2, −z + 1; #2, −x, −y + 1, −z; #3, −x + 1, −y, −z; #4, −x +
1, −y + 1, −z + 1.
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1991, 56, 4999.
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2000, 55b, 1015.
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Kozlowski, H. Z Naturforsch 1999, 54b, 1357.
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Mostaanzadeh, H. Polyhedron 2005, 24, 655.
[24] Narula, P. M.; Day, C. S.; Powers, B. A.; Odian, M. A.;
Lachgar, A.; Pennington, W. T.; Noftle, R. E. Polyhe-
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727882
(C17H24Cl2N3O2P),
CCDC
709119
(C19H28Cl2N3O2P), CCDC 727880 (C15H20Cl2N3O4P),
CCDC 727881 (C15H20Cl2N3O4P), and CCDC 709120
(C21H32Cl2N3O2P). Copies of the data may be ob-
tained, 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).
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