Different cyclic motifs in phospho-ric triamides containing a C(O)NHP(O)(NH)2 skeleton and an R22(10) graph set in three new compounds: A database analysis of hydrogen-bond strengths based on motifs

Article abstract of DOI:10.1107/S0108270111019755

In the crystal networks of N,N′-bis-(2-chloro-benzyl)- N′′-(2,6-difluoro-benzo-yl)phosphor-ic triamide, C ₂₁H₁₈Cl₂F₂N₃O ₂P, (I), N-(2,6-difluoro-benzo-yl)-N′,N′′-bis-(4- meth-oxy-benzyl)phosphor-ic triamide, C₂₃H₂₄F ₂N₃O₄P, (II), and N-(2-chloro-2,2-difluoro- acetyl)-N′,N′′-bis-(4-methyl-phenyl)phosphor-ic tri-amide, C₁₆H₁₇ClF₂N₃O₂P, (III), C=O...H-NC(O)NHP(O) and P=O...H-Namide hydrogen bonds are responsible for the aggregation of the mol-ecules. This is the opposite result from that commonly observed for carbacyl-amido-phosphates, which show a tendency for the phosphoryl group, rather than the carbonyl counterpart, to form hydrogen bonds with the NH group of the C(O)NHP(O) skeleton. This hydrogen-bond pattern leads to cyclic R₂ ²(10) motifs in (I)-(III), different from those found for all previously reported compounds of the general formula RC(O)NHP(O)[NR ¹ R ²]2 with the syn orientation of P=O versus NH [R₂ ²(8)], and also from those commonly observed for RC(O)NHP(O)[NHR ¹]₂ [a sequence of alternate R ₂ ²(8) and R₂ ²(12) motifs]. In these cases, the R₂ ²(8) and R₂ ²(12) graph sets are formed through similar kinds of hydrogen bond, i.e. a pair of P=O...H-NC(O)NHP(O) hydrogen bonds for the former and two C=O...H-Namide hydrogen bonds for the latter. This article also reviews 102 similar structures deposited in the Cambridge Structural Database and with the Inter-national Union of Crystallography, with the aim of comparing hydrogen-bond strengths in the above-mentioned cyclic motifs. This analysis shows that the strongest N-H...O hydrogen bonds exist in the R₂ ²(8) rings of some mol-ecules. The phosphoryl and carbonyl groups in each of compounds (I)-(III) are anti with respect to each other and the P atoms are in a tetra-hedral coordination environment. In the crystal structures, adjacent mol-ecules are linked via the above-mentioned hydrogen bonds in a linear arrangement, parallel to [010] for (I) and (III) and parallel to [100] for (II). Formation of the NC(O)NHP(O)-H...O=C instead of the NC(O)NHP(O)- H...O=P hydrogen bond is reflected in the higher NC(O)NHP(O)-H vibrational frequencies for these mol-ecules compared with previously reported analogous compounds.

Full text of DOI:10.1107/S0108270111019755

organic compounds
Acta Crystallographica Section C
Crystal Structure
linked via the above-mentioned hydrogen bonds in a linear
arrangement, parallel to [010] for (I) and (III) and parallel to
Communications
[100] for (II). Formation of the NC(O)NHP(O)—Hꢀ ꢀ ꢀO
C
ISSN 0108-2701
instead of the NC(O)NHP(O)—Hꢀ ꢀ ꢀO P hydrogen bond is
reflected in the higher NC(O)NHP(O)—H vibrational frequencies
for these molecules compared with previously reported
analogous compounds.
Different cyclic motifs in phosphoric
triamides containing a C(O)NHP(O)-
(NH)2 skeleton and an R22(10) graph
set in three new compounds: a data-
base analysis of hydrogen-bond
strengths based on motifs
Comment
In a recently published paper by Toghraee et al. (2011), the
patterns of hydrogen bonds were studied in the crystal packing
of phosphoric triamides (PTAs) containing a C(O)NHP(O)
skeleton. The authors classified this category of phosphor-
amide compounds into different subclasses with C(O)NH-
P(O)(N)2 and C(O)NHP(O)(NH)2 moieties, denoted sub-
classes A and B, respectively. It was found that the phosphoryl
group is a better donor than the carbonyl counterpart, so that
in all deposited CIF files in the Cambridge Structural Data-
base (CSD, Version 5.32, November 2010 update; Allen, 2002)
belonging to subclass A, only the POꢀ ꢀ ꢀH—N hydrogen bond
was observed in the crystal packing. When the P O group
and N—H unit are syn with respect to one another, this type of
hydrogen bond forms a hydrogen-bonded dimer [R22(8) ring;
for graph-set notation, see Bernstein et al. (1995)] (Fig. 1).
Moreover, for most cases of compounds in subclass B, the NH
group of the C(O)NHP(O) moiety is hydrogen bonded to
P(O), whereas the H atom of the NHR0 unit is involved in a
hydrogen-bond interaction with C(O). These interactions
usually produce two different kinds of centrosymmetric cyclic
motifs, viz. R22(8) and R22(12), which are alternate in a linear
arrangement. The R22(8) motif is formed through a pair of
NC(O)NHP(O)—Hꢀ ꢀ ꢀO P hydrogen bonds, while the R22(12)
ring is built via two C Oꢀ ꢀ ꢀH—Namide hydrogen bonds
(Fig. 2). Among the published structures, the C Oꢀ ꢀ ꢀH—
NC(O)NHP(O) interaction was found for only two examples, i.e.
C6H5C(O)NHP(O)[NHCH2C6H5]2 (Gholivand et al., 2006)
and C6H5C(O)NHP(O)[NHC6H11]2 (Pourayoubi, Rostami
Chaijan et al., 2011a). However, the existence of the
POꢀ ꢀ ꢀHNR0 interaction has been observed for four
compounds as a PO[ꢀ ꢀ ꢀHNC(O)NHP(O)][ꢀ ꢀ ꢀHNR0] (Gubina et
al., 2009; Gholivand, Shariatinia, Mashhadi et al., 2009) and a
PO[ꢀ ꢀ ꢀHNR0]2 hydrogen bond (Gholivand et al., 2006; Pour-
Mehrdad Pourayoubi,a* Atekeh Tarahhomi,a Anahid
Saneei,a Arnold L. Rheingoldb and James A. Golenb
aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad 91779, Iran,
and bDepartment of Chemistry, University of California, San Diego, 9500 Gilman
Drive, La Jolla, CA 92093, USA
Correspondence e-mail: mehrdad_pourayoubi@yahoo.com
Received 8 February 2011
Accepted 24 May 2011
Online 29 June 2011
In the crystal networks of N,N0-bis(2-chlorobenzyl)-N00-(2,6-
difluorobenzoyl)phosphoric triamide, C21H18Cl2F2N3O2P, (I),
N-(2,6-difluorobenzoyl)-N0,N00-bis(4-methoxybenzyl)phos-
phoric triamide, C23H24F2N3O4P, (II), and N-(2-chloro-
2,2-difluoroacetyl)-N0,N00-bis(4-methylphenyl)phosphoric tri-
amide, C16H17ClF2N3O2P, (III), C Oꢀ ꢀ ꢀH—NC(O)NHP(O) and
P
Oꢀ ꢀ ꢀH—Namide hydrogen bonds are responsible for the
aggregation of the molecules. This is the opposite result from
that commonly observed for carbacylamidophosphates, which
show a tendency for the phosphoryl group, rather than the
carbonyl counterpart, to form hydrogen bonds with the NH
group of the C(O)NHP(O) skeleton. This hydrogen-bond
pattern leads to cyclic R22(10) motifs in (I)–(III), different from
those found for all previously reported compounds of the
general formula RC(O)NHP(O)[NR1R2]2 with the syn orien-
tation of P O versus NH [R22(8)], and also from those
commonly observed for RC(O)NHP(O)[NHR1]2 [a sequence
of alternate R22(8) and R22(12) motifs]. In these cases, the R22(8)
and R22(12) graph sets are formed through similar kinds of
hydrogen bond, i.e. a pair of P Oꢀ ꢀ ꢀH—NC(O)NHP(O)
hydrogen bonds for the former and two C Oꢀ ꢀ ꢀH—Namide
hydrogen bonds for the latter. This article also reviews 102
similar structures deposited in the Cambridge Structural
Database and with the International Union of Crystal-
lography, with the aim of comparing hydrogen-bond strengths
in the above-mentioned cyclic motifs. This analysis shows that
the strongest N—Hꢀ ꢀ ꢀO hydrogen bonds exist in the R22(8)
rings of some molecules. The phosphoryl and carbonyl groups
in each of compounds (I)–(III) are anti with respect to each
other and the P atoms are in a tetrahedral coordination
environment. In the crystal structures, adjacent molecules are
Figure 1
The R22(8) graph set in compounds containing a C(O)NHP(O)(N)2
skeleton and a syn orientation of P O versus NH.
Acta Cryst. (2011). C67, o265–o272
doi:10.1107/S0108270111019755
# 2011 International Union of Crystallography o265

organic compounds
ayoubi, Rostami Chaijan et al., 2011a), where the O atoms act
as double hydrogen-bond acceptors (Steiner, 2002).
We present here the three new compounds, N,N0-bis(2-
chlorobenzyl)-N00-(2,6-difluorobenzoyl)phosphoric triamide,
(I), N-(2,6-difluorobenzoyl)-N0,N00-bis(4-methoxybenzyl)phos-
phoric triamide, (II), and N-(2-chloro-2,2-difluoroacetyl)-
N0,N00-bis(4-methylphenyl)phosphoric triamide, (III), which
show relatively rare C Oꢀ ꢀ ꢀH—NC(O)NHP(O) and P Oꢀ ꢀ ꢀ
H—Namide hydrogen bonds. In addition, we attempted to
analyse the strength of the hydrogen bonds based on their
motifs, and also to find a relationship between the N—H
stretching frequency and the hydrogen-bond pattern.
Figure 2
A view of the R22(8) and R22(12) motifs in compounds containing a
C(O)NHP(O)(NH)2 skeleton.
Figure 3
The molecular structure and atom-labelling scheme for (I). Displacement
ellipsoids are drawn at the 50% probability level.
102.33 (13)–116.04 (12)ꢁ, while the P—N bond lengths range
˚
from 1.616 (2) to 1.707 (2) A (Table 1). The phosphoryl and
carbonyl groups adopt an anti relationship in these structures,
which is in agreement with all previously reported acyclic
phosphoramidate compounds (Gholivand & Pourayoubi,
2004; Gholivand, Shariatinia, Mashhadi et al., 2009) containing
a C(O)NHP(O)(NH)2 skeleton. This conformation is the
opposite of the orientation of P(O) and C(O) groups in the
diazaphosphorinanes CCl3C(O)NHP(O)X (X = NHC10H6NH;
Gholivand, Shariatinia, Ansar et al., 2009), 4-F-C6H4C(O)-
NHP(O)X [X = NHCH2C(CH3)2CH2NH; Tarahhomi et al.,
2011] and CCl2HC(O)NHP(O)X [X = NHCH2C(CH3)2-
CH2NH; Toghraee et al., 2011], and a few examples of
compounds with the formula RC(O)NHP(O)[NR1R2]2, which
show a gauche orientation of P O versus C O (Toghraee et
al., 2011).
For compounds (I)–(III), single crystals were obtained at
room temperature from a 1:2 mixture of CH3OH/CHCl3 for
(I) and (II), and from a 1:4 mixture of CH3CN/CH3OH for
(III). Their molecular structures are shown in Figs. 3, 4 and 5,
respectively. The P atoms exhibit a distorted tetrahedral
environment, as has been noted for other phosphoric tri-
amides and their chalco-derivatives (Rudd et al., 1996). For
example, in (I), the bond angles at the P atom vary in the range
˚
The P O bond lengths are standard in (I) [1.475 (2) A],
˚
(II) [1.4804 (12) A] and (III) [1.475 (4) A]. As expected, the
˚
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o266 Pourayoubi et al. C21H18Cl2F2N3O2P, C23H24F2N3O4P and C16H17ClF2N3O2P
Acta Cryst. (2011). C67, o265–o272

organic compounds
Figure 6
Two types of R22(10) graph sets in compounds containing a C(O)NH-
P(O)(NH)2 skeleton.
Figure 4
The molecular structure and atom-labelling scheme for (II). Displace-
ment ellipsoids are drawn at the 50% probability level.
P—Namide bond lengths in all three compounds were found to
be significantly shorter than the related P—NC(O)NHP(O) bond
lengths (Tables 1, 3 and 5).
In (I) and (II), the chemical natures of the N atoms in both
compounds are different, so that the N atom of one benzyl-
amido moiety exhibits a slight deviation from planarity, while
Figure 7
A crystal packing diagram for (I). H atoms bound to C atoms have been
omitted for clarity. The P Oꢀ ꢀ ꢀH—Namide (marked a), C Oꢀ ꢀ ꢀH—
NC(O)NHP(O) (marked b) and Fꢀ ꢀ ꢀH—NC(O)NHP(O) (marked c) hydrogen
bonds are shown. [Colour key for the electronic version of the paper: red,
black and violet dashed lines, respectively. Additionally, O atoms are red,
amide N atoms are dark blue, NC(O)NHP(O) atoms are light blue, F atoms
are green–yellow and H atoms are light grey.]
Figure 5
The molecular structure and atom-labelling scheme for (III). Displace-
ment ellipsoids are drawn at the 50% probability level.
ꢂ
Acta Cryst. (2011). C67, o265–o272
Pourayoubi et al.
C21H18Cl2F2N3O2P, C23H24F2N3O4P and C16H17ClF2N3O2P o267

organic compounds
the N atoms of the benzoylamido and the other benzylamido
moiety have a practically planar environment. In (III), the
environments of all three N atoms are nearly planar. None of
these N atoms acts in any hydrogen bond as an acceptor, thus
exhibiting low Lewis base character. As expected, the C—
NC(O)NHP(O) bonds for these structures are shorter than the
other C—Namide bonds.
In the structures of (I)–(III), adjacent molecules are linked
C hydrogen bonds and also
via
NC(O)NHP(O)—Hꢀ ꢀ ꢀO
through two different Namide—Hꢀ ꢀ ꢀO P hydrogen bonds
involving the same pair of molecules (Tables 2, 4 and 6),
building R22(10) rings (Fig. 6a) in a linear arrangement, parallel
to [010] for (I) and (III) [for example, see Fig. 7 for compound
(I)] and parallel to [100] for (II) (Fig. 8). This means that, in
each of these structures, the phosphoryl group acts as a double
hydrogen-bond acceptor to form a P O[ꢀ ꢀ ꢀH—Namide 2
]
grouping. Another type of R22(10) graph set, forming by co-
operation of NC(O)NHP(O)—Hꢀ ꢀ ꢀO(P) and Namide—Hꢀ ꢀ ꢀO(C)
hydrogen bonds, is observed for diazaphosphorinane
CHCl2C(O)NHP(O)X [X = HNCH2C(CH3)2CH2NH; Togh-
raee et al., 2011] (Fig. 6b).
This hydrogen-bond pattern is the opposite of that
commonly observed for carbacylamidophosphates, which
show a tendency for the phosphoryl group, rather than the
carbonyl counterpart, to form hydrogen bonds with the more
acidic NH group of the C(O)NHP(O) skeleton, whereas the
NH group of the NHR0 unit is hydrogen bonded to C(O).
Exceptions to this bonding selectivity in these structures
may be attributed to kinetic factors controlling the crystal
growth (MacDonald & Whitesides, 1994).
Figure 8
A crystal packing diagram for (II). H atoms bound to C atoms have been
A search for phosphoric triamides with a C(O)NHP(O)
skeleton in the CSD and recently published papers (Pour-
ayoubi, Tarahhomi et al., 2010a,b, 2011; Pourayoubi, Rostami
Chaijan et al., 2011a,b; Pourayoubi & Saneei, 2011; Pour-
ayoubi, Toghraee & Divjakovic, 2011; Raissi Shabari et al.,
2011; Tarahhomi et al., 2011; Toghraee et al., 2011) shows that
the strongest N—Hꢀ ꢀ ꢀO hydrogen bonds are found for
omitted for clarity. The P Oꢀ ꢀ ꢀH—Namide (marked a) and C Oꢀ ꢀ ꢀH—
N
C(O)NHP(O) (marked b) hydrogen bonds are shown. (Colour key for the
electronic version of the paper: red and black dashed lines, respectively;
the atomic colour scheme is the same as for Fig. 7.)
P
Oꢀ ꢀ ꢀH—NC(O)NHP(O) hydrogen bonds, especially in the
R22(8) rings of some molecules [in the case of a syn orientation
of P O versus N—H which allows the building of the cyclic
motif through a pair of P Oꢀ ꢀ ꢀH—NC(O)NHP(O) hydrogen
bonds]. A histogram of the Nꢀ ꢀ ꢀO distances in these N—
Hꢀ ꢀ ꢀO hydrogen bonds is given in Fig. 9. The strongest (two
columns on the left) and weakest (two columns on the right)
hydrogen bonds are shown for Nꢀ ꢀ ꢀO distances in the ranges
˚
˚
2.70–2.80 A [for NC(O)NHP(O)–Hꢀ ꢀ ꢀO(P) hydrogen bonds] and
3.00–3.10 A [for Namide–Hꢀ ꢀ ꢀO(C) hydrogen bonds], while in
˚
the range 2.80–3.00 A for donor–acceptor distances both types
of hydrogen bond are found.
Figure 9
In (I), besides co-operation in the N—Hꢀ ꢀ ꢀO hydrogen
bond, the benzamide N—H group is involved in an intra-
molecular N1—H1Nꢀ ꢀ ꢀF1 hydrogen bond (Table 2). Further
stabilization of (I) is produced via a weak C11—H11Aꢀ ꢀ ꢀF2iii
A histogram of Nꢀ ꢀ ꢀO distances in N—Hꢀ ꢀ ꢀO hydrogen bonds for
phosphoric triamides with a C(O)NHP(O) skeleton (for an N—Hꢀ ꢀ ꢀO
angle more than 110ꢁ). The data shown in the first two and last two
columns (brown and red, respectively, in the electronic version of the
paper) were observed for NC(O)NHP(O)—Hꢀ ꢀ ꢀO and Namide—Hꢀ ꢀ ꢀO
hydrogen bonds, respectively. Both types of hydrogen bond were
i
i
˚
hydrogen bond and C O1ꢀ ꢀ ꢀF1 [O1ꢀ ꢀ ꢀF1 = 2.876 (3) A;
symmetry code: (i) x, y + 1, z] and Cl2ꢀ ꢀ ꢀCl2iv [3.258 (1) A;
˚
˚
observed in the range 2.80–3.00 A (central four columns, light brown).
Only one Namide—Hꢀ ꢀ ꢀO and one NC(O)NHP(O)—Hꢀ ꢀ ꢀO hydrogen bond,
symmetry code: (iv) ꢃx, ꢃy + 2, ꢃz + 1] intermolecular inter-
˚
respectively, are found in the ranges 2.80–2.85 and 2.95–3.00 A.
actions.
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o268 Pourayoubi et al. C21H18Cl2F2N3O2P, C23H24F2N3O4P and C16H17ClF2N3O2P
Acta Cryst. (2011). C67, o265–o272

organic compounds
Figure 10
A partial crystal packing diagram for (II), viewed parallel to the bc plane, formed via intermolecular C—Hꢀ ꢀ ꢀF and C—Hꢀ ꢀ ꢀO hydrogen bonds (the N—
Hꢀ ꢀ ꢀO hydrogen bonds are along the a axis). H atoms involved in contacts are shown as light grey and the other H atoms have been omitted for clarity.
iv
methoxy
vi
The C15methoxy—H15Aꢀ ꢀ ꢀF1iii (marked a), C13—H13Aꢀ ꢀ ꢀO3
(marked b), C3—H3Bꢀ ꢀ ꢀ(O2)P1v (marked c) and C16—H16Bꢀ ꢀ ꢀO4
(marked
methoxy
d) hydrogen bonds are shown (colour key for the electronic version of the paper: black, orange, purple and blue dashed lines, respectively). The
symmetry codes are as in Table 4.
The hydrogen-bond pattern in (II) is complicated. A pair of
C15methoxy—H15Aꢀ ꢀ ꢀF1iii hydrogen bonds make an R22(30)
one Cmethoxy—Hꢀ ꢀ ꢀF and one C3—H3Bꢀ ꢀ ꢀ(O2)P1v hydrogen
bond forms R33(16) rings. Moreover, the cyclic dimer motif is
composed of a pair of intermolecular C—Hꢀ ꢀ ꢀOmethoxy
hydrogen bonds forming a centrosymmetric R22(8) ring
(Fig. 10). Also, a trimer motif, viz. an R33(27) ring (Fig. 10), is
compounds may be a result of these different hydrogen-bond
patterns. For example, in the compounds 2-NO2–C6H4-
C(O)NHP(O)[N(C2H5)2]2 (Gholivand et al., 2010) and
Cl3CC(O)NHP(O)[NHC(CH3)3]2 (Gholivand & Pourayoubi,
2004), the NC(O)NHP(O)—H stretching frequencies, which are
involved in the NC(O)NHP(O)—Hꢀ ꢀ ꢀO(P) hydrogen bond,
appear at 3030 and 3045 cmꢃ1, respectively, while no absorp-
tion bands for N—H stretching frequencies are observed
below 3180 cmꢃ1 in any of (I)–(III). In (I), three absorption
bands are revealed at 3204, 3262 and 3345 cmꢃ1, while for (II),
with hydrogen bonds of fairly similar strengths, the N—H
stretching modes overlap and only one absorption band
appears at 3263 cmꢃ1. For (III), the absorption bands at 3260
and 3183 cmꢃ1 are assigned to the N—H stretching modes.
iv
methoxy
ring, whereas a combination of one C13—H13Aꢀ ꢀ ꢀO3
,
formed through a combination of two intermolecular C16—
H16Bꢀ ꢀ ꢀO4
vi
methoxy
and one C—Hꢀ ꢀ ꢀ(O)P hydrogen bond.
These hydrogen bonds expand the crystal structure of (II) into
a three-dimensional arrangement. A weak C7 O1ꢀ ꢀ ꢀF1i
i
˚
[O1ꢀ ꢀ ꢀF1 = 2.986 (2) A; symmetry code: (i) x + 1, y, z] inter-
action is also found in the crystal packing. The crystal packing
of (III) does not show any C—Hꢀ ꢀ ꢀX (X = O, F or Cl) inter-
actions.
In a paper by Tarahhomi et al. (2011), the effect of lowering
the NC(O)NHP(O)—H vibrational frequency by strong
NC(O)NHP(O)—Hꢀ ꢀ ꢀO P hydrogen bonds was discussed, so
that a compound with a stronger N—Hꢀ ꢀ ꢀO hydrogen bond
showed a lower N—H vibrational frequency. Moreover, the
NC(O)NHP(O)—H stretching mode appeared at a lower
frequency than that of Namide—H.
The differences in the N—H regions in the IR spectroscopic
data of (I)–(III) from those of previously reported analogous
Experimental
2,6-F2-C6H3C(O)NHP(O)Cl2 and CClF2C(O)NHP(O)Cl2 were pre-
pared according to the literature methods reported by Pourayoubi,
Tarahhomi et al. (2010a) and Iriarte et al. (2008), respectively.
Compound (I) was synthesized from the reaction of 2,6-F2-
C6H3C(O)NHP(O)Cl2 (0.35 g, 1.28 mmol) and 2-chlorobenzylamine
(0.725 g, 5.12 mmol) in dry chloroform (30 ml). After stirring for 6 h,
the solvent was evaporated and the product was washed with distilled
water and recrystallized from a 1:2 (v/v) mixture of methanol and
ꢂ
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Pourayoubi et al.
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organic compounds
chloroform at room temperature. IR (KBr, ꢀ, cmꢃ1): 3345 (NH), 3262
(NH), 3204 (NH), 2925, 1668 (C O), 1623, 1470, 1426, 1287, 1236,
1205, 1127, 1090, 1049, 1041, 1011, 902, 817, 769, 753, 694, 584, 510,
578.
Table 3
Selected geometric parameters (A, ) for (II).
ꢁ
˚
P1—O2
P1—N3
P1—N2
P1—N1
1.4804 (12)
1.6141 (14)
1.6263 (14)
1.7084 (14)
O1—C7
N1—C7
N2—C8
N3—C16
1.225 (2)
1.355 (2)
1.465 (2)
1.461 (2)
Compound (II) was synthesized by a similar method to (I), but
using 4-methoxybenzylamine (0.598 g, 4.36 mmol) instead of
2-chlorobenzylamine [2,6-F2-C6H3C(O)NHP(O)Cl2: 0.30 g, 1.09 mmol].
Single crystals suitable for X-ray crystallography were obtained after
recrystallization from a 1:2 (v/v) mixture of methanol and chloroform
at room temperature. IR (KBr, ꢀ, cmꢃ1): 3263 (NH), 3003, 2958, 1668
(C O), 1623, 1589, 1515, 1466, 1441, 1303, 1253, 1197, 1078, 1042,
1007, 923, 813, 788, 764, 698, 588, 523, 478.
O2—P1—N3
O2—P1—N2
N3—P1—N2
O2—P1—N1
N3—P1—N1
114.12 (7)
117.74 (7)
103.24 (7)
102.89 (7)
112.12 (7)
N2—P1—N1
C7—N1—P1
C8—N2—P1
C16—N3—P1
O1—C7—N1
106.75 (7)
125.50 (11)
121.68 (12)
124.33 (12)
123.24 (15)
Compound (III) was synthesized from the reaction of CCl-
F2C(O)NHP(O)Cl2 (0.40 g, 1.6 mmol) in dry CHCl3 and a solution of
p-toluidine (0.343 g, 3.2 mmol) and triethylamine (0.324 g, 3.2 mmol)
in dry CHCl3 at 273 K. After stirring for 4 h, the solvent was
evaporated at room temperature. The solid product was washed with
water. Single crystals suitable for X-ray crystallography were
recrystallized from a 4:1 (v/v) mixture of methanol and acetonitrile by
slow evaporation at room temperature. IR (KBr, ꢀ, cmꢃ1): 3260
(NH), 3183 (NH), 2927, 1717 (C O), 1620, 1517, 1466, 1383, 1281,
1225, 1163, 1133, 963, 863, 813, 697.
O2—P1—N1—C7
N3—P1—N1—C7
ꢃ178.00 (13)
N2—P1—N1—C7
P1—N1—C7—O1
ꢃ53.42 (15)
ꢃ7.4 (2)
58.94 (15)
Table 4
Hydrogen-bond geometry (A, ) for (II).
ꢁ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Nꢀ ꢀ ꢀO1i
N2—H2Nꢀ ꢀ ꢀO2ii
N3—H3Nꢀ ꢀ ꢀO2ii
C3—H3Bꢀ ꢀ ꢀO2v
C13—H13Aꢀ ꢀ ꢀO3iv
C15—H15Aꢀ ꢀ ꢀF1iii
C16—H16Bꢀ ꢀ ꢀO4vi
0.84 (1)
0.83 (2)
0.83 (2)
0.95
0.95
0.98
2.07 (2)
2.04 (2)
2.15 (2)
2.61
2.8958 (18)
2.8414 (18)
2.9173 (18)
3.293 (2)
169 (2)
163 (2)
153 (2)
129
158
105
2.49
2.76
2.68
3.390 (3)
3.156 (2)
3.581 (2)
Compound (I)
0.99
151
Crystal data
3
˚
Symmetry codes: (i) x þ 1; y; z; (ii) x ꢃ 1; y; z; (iii) ꢃx; ꢃy þ 1; ꢃz þ 1; (iv) ꢃx; ꢃy þ 2,
C21H18Cl2F2N3O2P
Mr = 484.25
V = 2058.2 (4) A
Z = 4
1
1
3
2
ꢃz þ 1; (v) x; y ꢃ 1; z; (vi) ꢃx þ ; y ꢃ ; ꢃz þ .
2
2
Monoclinic, P21=c
Mo Kꢂ radiation
ꢃ = 0.44 mmꢃ1
T = 100 K
0.25 ꢄ 0.10 ꢄ 0.10 mm
˚
a = 19.643 (3) A
˚
b = 4.9874 (6) A
˚
c = 21.482 (3) A
Data collection
ꢁ = 102.056 (2)ꢁ
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
Tmin = 0.899, Tmax = 0.958
25048 measured reflections
4821 independent reflections
3463 reflections with I > 2ꢄ(I)
Rint = 0.074
Table 1
Selected geometric parameters (A, ) for (I).
ꢁ
˚
Refinement
P1—O2
P1—N2
P1—N3
P1—N1
1.475 (2)
1.616 (2)
1.632 (2)
1.707 (2)
O1—C7
N1—C7
N2—C8
N3—C15
1.227 (3)
1.355 (4)
1.457 (4)
1.465 (4)
R[F2 > 2ꢄ(F2)] = 0.052
wR(F2) = 0.128
S = 1.03
4821 reflections
289 parameters
3 restraints
H atoms treated by a mixture of
independent and constrained
refinement
ꢃ3
˚
Áꢅmax = 0.65 e A
ꢃ3
˚
Áꢅmin = ꢃ0.48 e A
O2—P1—N2
O2—P1—N3
N2—P1—N3
O2—P1—N1
N2—P1—N1
115.79 (12)
116.04 (12)
102.33 (13)
104.51 (11)
109.20 (12)
N3—P1—N1
C7—N1—P1
C8—N2—P1
C15—N3—P1
O1—C7—N1
108.83 (12)
123.5 (2)
123.93 (19)
120.01 (19)
121.7 (2)
Compound (II)
Crystal data
O2—P1—N1—C7
N2—P1—N1—C7
173.6 (2)
ꢃ61.9 (3)
N3—P1—N1—C7
P1—N1—C7—O1
49.1 (3)
2.6 (4)
3
˚
V = 2249.7 (5) A
Z = 4
C23H24F2N3O4P
Mr = 475.42
Monoclinic, P21=n
Mo Kꢂ radiation
ꢃ = 0.17 mmꢃ1
T = 100 K
0.22 ꢄ 0.10 ꢄ 0.10 mm
˚
a = 4.8252 (6) A
˚
b = 10.3456 (12) A
Table 2
Hydrogen-bond geometry (A, ) for (I).
˚
c = 45.068 (5) A
ꢁ
˚
ꢁ = 90.530 (2)ꢁ
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
Data collection
N1—H1Nꢀ ꢀ ꢀO1i
N1—H1Nꢀ ꢀ ꢀF1
N2—H2Nꢀ ꢀ ꢀO2ii
N3—H3Nꢀ ꢀ ꢀO2ii
0.85 (2)
0.85 (2)
0.83 (2)
0.83 (2)
2.04 (2)
2.44 (3)
2.32 (2)
2.08 (2)
2.858 (3)
2.881 (3)
3.092 (3)
2.869 (3)
162 (3)
113 (2)
154 (3)
161 (3)
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
Tmin = 0.963, Tmax = 0.983
18537 measured reflections
5131 independent reflections
4200 reflections with I > 2ꢄ(I)
Rint = 0.042
Symmetry codes: (i) x; y þ 1; z; (ii) x; y ꢃ 1; z.
ꢂ
o270 Pourayoubi et al. C21H18Cl2F2N3O2P, C23H24F2N3O4P and C16H17ClF2N3O2P
Acta Cryst. (2011). C67, o265–o272

organic compounds
˚
Table 5
Selected geometric parameters (A, ) for (III).
length restraint of 0.85 (2) A and with Uiso(H) = 1.2Ueq(N). The
positions of H atoms bound to C atoms were calculated and refined as
isotropic using an appropriate riding model; for compounds (I) and
ꢁ
˚
P1—O2
P1—N2
P1—N3
P1—N1
1.475 (4)
1.615 (5)
1.622 (4)
1.707 (5)
F1—C2
O1—C1
N1—C1
N2—C3
1.330 (6)
1.233 (6)
1.339 (7)
1.410 (7)
˚
(II), bond distances were 0.95, 0.99 and 0.98 A for CH, CH2 and CH3
groups, respectively, with riding constraints of 1.2Ueq(C) for CH and
CH2 groups, and 1.5Ueq(C) for CH3 groups. For compound (III), the
˚
distance values were 0.93 and 0.96 A for CH and CH3 groups,
respectively, with Uiso(H) = 1.2 and 1.5Ueq(C), respectively.
Data collection: APEX2 (Bruker, 2005) for (I) and (II); SMART
(Bruker, 1998) for (III). Cell refinement: SAINT (Bruker, 2005) for
(I) and (II); SAINT-Plus (Bruker, 1998) for (III). Data reduction:
SAINT for (I) and (II); SAINT-Plus for (III). For all compounds,
program(s) used to solve structure: SHELXS97 (Sheldrick, 2008);
program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury
(Macrae et al., 2008); software used to prepare material for publica-
tion: SHELXTL and enCIFer (Allen et al., 2004).
O2—P1—N2
O2—P1—N3
N2—P1—N3
O2—P1—N1
N2—P1—N1
116.7 (2)
117.1 (2)
102.1 (2)
104.2 (2)
108.5 (2)
N3—P1—N1
C1—N1—P1
C3—N2—P1
C10—N3—P1
O1—C1—N1
107.9 (2)
123.4 (4)
126.5 (4)
120.9 (3)
124.8 (5)
O2—P1—N1—C1
N2—P1—N1—C1
176.1 (4)
ꢃ58.9 (5)
N3—P1—N1—C1
P1—N1—C1—O1
51.0 (5)
3.3 (8)
Table 6
Hydrogen-bond geometry (A, ) for (III).
ꢁ
˚
The support of this investigation by Ferdowsi University of
Mashhad is gratefully acknowledged.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1ꢀ ꢀ ꢀO1i
N2—H2ꢀ ꢀ ꢀO2ii
N3—H3ꢀ ꢀ ꢀO2ii
0.86 (2)
0.85 (2)
0.84 (2)
2.05 (3)
2.19 (3)
2.20 (3)
2.877 (6)
2.986 (6)
2.972 (5)
163 (5)
158 (5)
153 (5)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: YP3002). Services for accessing these data are
described at the back of the journal.
Symmetry codes: (i) x; y ꢃ 1; z; (ii) x; y þ 1; z.
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5131 reflections
309 parameters
3 restraints
H atoms treated by a mixture of
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˚
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Mr = 387.75
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˚
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Acta Cryst. (2011). C67, o265–o272
Pourayoubi et al.
C21H18Cl2F2N3O2P, C23H24F2N3O4P and C16H17ClF2N3O2P o271

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o272 Pourayoubi et al. C21H18Cl2F2N3O2P, C23H24F2N3O4P and C16H17ClF2N3O2P
Acta Cryst. (2011). C67, o265–o272