N-(4-Nitro-benzo-yl)-N′-phenyl-hydrazine: a three-dimensional hydrogen-bonded framework

Article abstract of DOI:10.1107/S0108270107020628

In the title compound (systematic name: N-anilino-4-nitro-benzamide), C13H11N3O3, the mol-ecules are linked into a complex three-dimensional framework structure by a combination of two-centre N - H...O and C - H...O hydrogen bonds and a three-centre N - H

Full text of DOI:10.1107/S0108270107020628

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
conformationally chiral. The achiral space group ensures that
each crystal contains only a single enantiomeric form.
The molecules of compound (I) are linked into a complex
three-dimensional framework structure by a combination of
one two-centre NÐHÁ Á ÁO hydrogen bond, one rather asym-
metric three-centre NÐHÁ Á Á(O,N) hydrogen bond and two
independent two-centre CÐHÁ Á ÁO hydrogen bonds (Table 2).
The formation of the sheet is readily analysed in terms of
simple substructures.
ISSN 0108-2701
0
N-(4-Nitrobenzoyl)-N -phenyl-
hydrazine: a three-dimensional
hydrogen-bonded framework
In the ®rst substructure, amide atom N1 in the molecule at
(
x, y, z) acts as hydrogen-bond donor to amide atom O7 in the
molecule at (� 1 + x, y, z), so generating by translation a C(4)
Bernstein et al., 1995) chain running parallel to the [100]
a
b
James L. Wardell, John N. Low and Christopher
c
Glidewell *
(
direction (Fig. 2). In addition, atoms N2 and C26 in the mol-
ecule at (x, y, z) both act as hydrogen-bond donors to atom O7
a
Instituto de Qu Âõ mica, Departamento de Qu Âõ mica Inorg aà nica, Universidade Federal
b
do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, Department of Chemistry,
1
1
in the molecule at (� + x, 2 � y, 1 � z), so forming a
University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and
2
1
2
c
School of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
C(5)C(7)[R (6)] chain of rings running parallel to the [100]
1
direction and generated by the 2 screw axis along (x, , )
1
4 2
1
Correspondence e-mail: cg@st-andrews.ac.uk
(
Fig. 3). Atom N2 at (x, y, z) also forms a rather long and
1
Received 13 April 2007
Accepted 24 April 2007
Online 11 May 2007
1
probably fairly weak interaction with atom N2 at (� + x, � y,
2
2
In the title compound (systematic name: N-anilino-4-nitro-
benzamide), C H N O , the molecules are linked into a
1
3
11
3
3
complex three-dimensional framework structure by a combi-
nation of two-centre NÐHÁ Á ÁO and CÐHÁ Á ÁO hydrogen
bonds and a three-centre NÐHÁ Á Á(O,N) hydrogen bond.
Comment
As part of our continuing investigation of the supramolecular
structures of acylhydrazines and acylhydrazones, we report
here the structure of the title compound, (I) (Fig. 1), whose
supramolecular structure we compare with that of the related
Figure 1
A molecule of compound (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms are shown as small spheres of arbitrary radii.
0
compound N-(3,5-dinitrobenzoyl)-N -phenylhydrazine, (II)
(
Wardell et al., 2006).
The con®guration at each of atoms N1 and N2 of (I) is
almost coplanar. The central CÐC( O)ÐNÐN unit adopts
an almost planar trans conformation and the remainder of the
molecular conformation can be de®ned in terms of just four
further torsion angles (Table 1). The large C7ÐN1ÐN2ÐC21
torsion angle re¯ects the tendency of the lone-pair orbitals on
N1 and N2 to be nearly orthogonal in order to minimize the
corresponding overlap and resonance integrals. The molecules
have no internal symmetry in the solid state and are thus
Figure 2
A stereoview of part of the crystal structure of compound (I), showing the
formation of a hydrogen-bonded chain of rings running parallel to the
[100] direction. For the sake of clarity, H atoms not involved in the motif
shown have been omitted.
o334 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270107020628
Acta Cryst. (2007). C63, o334±o336

organic compounds
1
� z), so that N2 can be regarded as the donor in an asym-
[100], [010] and [001] (Figs. 2±4) suf®ces to generate a single
three-dimensional framework.
metric but almost planar three-centre NÐHÁ Á Á(O,N)
hydrogen bond. The combination of all these interactions
generates a complex chain of rings running parallel to the
In the related 3,5-dinitro compound, (II) (Wardell et al.,
2006), the molecules are again conformationally chiral, with a
ꢀ
[
100] direction (Fig. 2).
The second substructure is built from a single CÐHÁ Á ÁO
C7ÐN1ÐN2ÐC21 torsion angle of 84.2 (2) , but the
centrosymmetric space group P2 /n accommodates equal
1
hydrogen bond. Aryl atom C3 in the molecule at (x, y, z) acts
as hydrogen-bond donor to nitro atom O42 in the molecule at
numbers of the two enantiomeric forms. The molecules are
linked into sheets by a combination of three independent two-
centre hydrogen bonds, one each of NÐHÁ Á ÁO(carbonyl), NÐ
HÁ Á ÁO(nitro) and CÐHÁ Á ÁO(carbonyl) types.
1
3
(� x, � + y, � z), so forming a C(5) chain running parallel to
the [010] direction and generated by the 2 screw axis along
1
2
2
3
4
(
0, y, ) (Fig. 3).
In combination, the NÐHÁ Á ÁO and CÐHÁ Á ÁO hydrogen
Experimental
bonds, which individually generate two independent C(5)
helical chains running parallel to [100] and [010], respectively,
A solution of 4-nitrobenzoyl chloride (2 mmol) and phenylhydrazine
(4 mmol) in 1,2-dichloroethane (25 ml) was heated under re¯ux for
2
2
together generate a C (16) chain running parallel to the [001]
direction (Fig. 4). The combined action of chains parallel to
3
h. The reaction mixture was cooled and the solvent was removed
under reduced pressure. The solid product was then recrystallized
from ethanol to give the title compound, (I) [m.p. 476±478 K;
literature values: 476±478 (Kornet et al., 1986) and 471±473 K (Wang
et al., 2005)].
Crystal data
Ê
V = 1202.7 (3) A
3
C
13
H N
11 3
O
3
M
r
= 257.25
Orthorhombic, P2 2 2
1 1
Z = 4
Mo Kꢀ radiation
ꢁ = 0.10 mm
T = 120 (2) K
1
Ê
� 1
a = 4.6982 (6) A
b = 9.9532 (13) A
Ê
c = 25.719 (4) A
Ê
0.32 Â 0.16 Â 0.07 mm
Data collection
Bruker Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
4443 measured re¯ections
1477 independent re¯ections
1314 re¯ections with I > 2ꢂ(I)
Figure 3
Rint = 0.037
Part of the crystal structure of compound (I), showing the formation of a
hydrogen-bonded C(5) chain running parallel to the [010] direction.
Atoms marked with an asterisk (*) or a hash (#) are at the symmetry
Tmin = 0.975, Tmax = 0.993
Re®nement
2
1
2
3
2
1
3
positions (� x, � + y, � z) and (� x, 2 + y, 2 � z), respectively. For the
2
R[F > 2ꢂ(F )] = 0.054
wR(F ) = 0.149
172 parameters
H-atom parameters constrained
sake of clarity, H atoms not involved in the motif shown have been
omitted.
2
Ê
� 3
Áꢃmax = 0.27 e A
S = 1.10
477 re¯ections
1
Áꢃmin = � 0.27 e AÊ
� 3
Table 1
Selected torsion angles ( ).
ꢀ
C2ÐC1ÐC7ÐN1
C1ÐC7ÐN1ÐN2
C7ÐN1ÐN2ÐC21
27.5 (5)
179.3 (3)
81.7 (4)
N1ÐN2ÐC21ÐC22
C3ÐC4ÐN4ÐO41
� 11.2 (5)
8.7 (6)
Table 2
Hydrogen-bond geometry (A, ).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
i
N1ÐH1Á Á ÁO7
0.88
0.88
0.88
0.95
0.95
2.18
2.14
2.62
2.52
2.50
2.926 (4)
2.952 (4)
3.302 (4)
3.419 (5)
3.285 (5)
143
154
135
158
140
ii
N2ÐH2AÁ Á ÁO7
ii
N2ÐH2AÁ Á ÁN2
iii
C3ÐH3Á Á ÁO42
ii
C26ÐH26Á Á ÁO7
1
2
1
2
1
2
3
2
Symmetry codes: (i) x � 1; y; z; (ii) x � ; � y ‡ ; � z ‡ 1; (iii) � x; y � ; � z ‡ .
Figure 4
A stereoview of part of the crystal structure of compound (I), showing the
2
formation of a hydrogen-bonded C (16) chain running parallel to the
[001] direction. For the sake of clarity, H atoms not involved in the motif
shown have been omitted.
2
1 1 1
The space group P2 2 2 was uniquely assigned from the
systematic absences. All H atoms were located in difference maps and
ꢁ
Acta Cryst. (2007). C63, o334±o336
Wardell et al.
C H N
13 11 3
O
3
o335

organic compounds
Ê
Ê
then treated as riding atoms, with CÐH = 0.95 A and NÐH = 0.88 A,
and with Uiso(H) = 1.2Ueq(C,N). In the absence of signi®cant resonant
scattering, it was not possible to determine the absolute con®guration
of the molecules in the crystal selected for data collection. However,
this has no chemical signi®cance and the Friedel-equivalent re¯ec-
tions were merged prior to the ®nal re®nements.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ3075). Services for accessing these data are
described at the back of the journal.
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The X-ray data were collected at the EPSRC National
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thanks CNPq and FAPERJ for ®nancial support.
ꢁ
o336 Wardell et al.
C H N
13 11 3
O
3
Acta Cryst. (2007). C63, o334±o336