2-Nitrophenoxyacetanilide: A chain of rings generated by C - H...O hydrogen bonds

Article abstract of DOI:10.1107/S010827010400513X

The crystal structure of 2-Nitrophenoxyacetanilide with conformation dominated by an intramolecular N-H···O hydrogen bond having one of the nitro O atoms as acceptor was discussed. The molecules in these compounds were linked by paired C-H··· hydrogen bonds. The presence of two independent aryl groups offered the possibility of N-H···π(arene) and C- H···π(arene) hydrogen bonding together with aromatic π-π stacking interactions. The supramolecular aggregation was determined by two C-H··· hydrogen bonds, one weaker than the other.

Full text of DOI:10.1107/S010827010400513X

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
2-Nitrophenoxyacetanilide: a chain
of rings generated by CÐHÁ Á ÁO
hydrogen bonds
Christopher Glidewell,a* John N. Low,b Janet M. S.
Skakleb and James L. Wardellc
Figure 1
The molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland,
bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
c
Â
Â
AB24 3UE, Scotland, and Instituto de Quõmica, Departamento de Quõmica
Ã
Inorganica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro,
hydrogen bond, so forming an S(9) motif (Bernstein et al.,
1995). In addition, there is a short contact to atom O2, but this
contact is probably just an adventitious consequence of the
hydrogen bond to atom O11. The consequences of the intra-
molecular hydrogen bonding are ®rstly the nearly planar
overall conformation (Table 1), with a cisoid O2ÐC27Ð
C28ÐN2 fragment, and secondly the unavailability of the NH
group for participation in intermolecular hydrogen bonds. The
bond angles in the central spacer unit are indicative of the
strongly attractive nature of the intramolecular hydrogen
bond. The dihedral angle between the nitro group and the
adjacent aryl ring is 11.8 (2)ꢀ.
The supramolecular aggregation is determined by two CÐ
HÁ Á ÁO hydrogen bonds, one weaker than the other (Table 2).
In the stronger of these two interactions, aromatic atom C3 in
the molecule at (x, y, z) acts as a hydrogen-bond donor to
carbonyl atom O28 in the molecule at (1 x, 1 y, 1 z), so
forming a centrosymmetric S(9)[R22(14)]S(9) (Bernstein et al.,
1995) dimer centred at (12, 21, 21 ) (Fig. 2). These dimers are linked
by the longer of the two intermolecular hydrogen bonds; atom
C27 in the molecule at (x, y, z) acts as a donor via atom H27A
RJ, Brazil
Correspondence e-mail: cg@st-andrews.ac.uk
Received 3 March 2004
Accepted 4 March 2004
Online 31 March 2004
In molecules of the title compound, C14H12N2O4, the
conformation is dominated by an intramolecular NÐHÁ Á ÁO
hydrogen bond in which one of the nitro O atoms is the
acceptor. The molecules are linked by paired CÐHÁ Á ÁO
Ê
Ê
hydrogen bonds [HÁ Á ÁO = 2.41 A, CÁ Á ÁO = 3.2990 (17) A and
CÐHÁ Á ÁO = 156ꢀ] into centrosymmetric R22(14) dimers; these
dimers are linked weakly into chains of alternating R22(14) and
R44(40) rings by a second CÐHÁ Á ÁO hydrogen bond [HÁ Á ÁO =
ꢀ
Ê
Ê
2.55 A, CÁ Á ÁO = 3.5006 (15) A and CÐHÁ Á ÁO = 162 ].
Comment
The title compound, (I) (Fig. 1), was designed to contain a
wide variety of potential donors and acceptors of both hard
and soft (Braga et al., 1995; Desiraju & Steiner, 1999)
hydrogen bonds. Thus, there are both NÐH and CÐH bonds
to provide potential hydrogen-bond donors, and there are
three types of O-atom sites as potential acceptors, namely the
ether O, the carbonyl O and the nitro O atoms. In addition, the
presence of two independent aryl groups offers the possibility
of NÐHÁ Á Áꢀ(arene) and CÐHÁ Á Áꢀ(arene) hydrogen bonding,
as well as aromatic ꢀ±ꢀ stacking interactions.
Figure 2
Part of the crystal structure of (I), showing the formation of a
centrosymmetric hydrogen-bonded dimer. For clarity, the unit-cell box
and H atoms bonded to C atoms not involved in the motif shown have
been omitted. Atoms marked with an asterisk (*) are at the symmetry
position (1 x, 1 y, 1 z).
In the event, the only hard hydrogen bond is intramol-
ecular, and this appears to be the dominant in¯uence on the
overall molecular conformation. Amine atom N2 acts as a
donor to nitro atom O11 in a nearly linear NÐHÁ Á ÁO
o290 # 2004 International Union of Crystallography
DOI: 10.1107/S010827010400513X
Acta Cryst. (2004). C60, o290±o292

organic compounds
Re®nement
to nitro atom O11 in the molecule at (x, 1 + y, z), so forming
by translation a C(7) chain parallel to [010]. Propagation of
this hydrogen bond by translation and inversion then gener-
ates a complex chain of rings running parallel to the [010]
direction, in which R22(14) rings centred at (12, 21 + n, 12 ) (n = zero
or integer) alternate with R44(40) rings centred at (21, n, 12 ) (n =
zero or integer) (Fig. 3).
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.040
wR(F2) = 0.108
S = 1.05
2869 re¯ections
182 parameters
H-atom parameters constrained
w = 1/[ꢆ2(F2o) + (0.0596P)2
+ 0.0301P]
where P = (F2o + 2Fc2)/3
(Á/ꢆ)max = 0.001
Áꢇmax = 0.23 e A
3
Ê
3
Ê
0.19 e A
Áꢇmin
=
Extinction correction: SHELXL97
Extinction coef®cient: 0.015 (2)
Table 1
Selected geometric parameters (ꢀ).
C2ÐO2ÐC27
O2ÐC27ÐC28
118.86 (9)
108.62 (9)
C27ÐC28ÐN2
C28ÐN2ÐC21
115.33 (11)
128.99 (11)
O2ÐC27ÐC28ÐN2
C27ÐC28ÐN2ÐC21
C28ÐN2ÐC21ÐC22
8.14 (15)
178.80 (12)
9.4 (2)
C28ÐC27ÐO2ÐC2
C1ÐC2ÐO2ÐC27
C2ÐC1ÐN1ÐO11
167.20 (10)
168.01 (11)
12.48 (18)
Figure 3
Table 2
Hydrogen-bonding geometry (A, ).
A stereoview of part of the crystal structure of (I), showing the formation
of a chain of alternating R22(14) and R44(40) rings along [010]. For clarity, H
atoms bonded to C atoms not involved in the motifs shown have been
omitted.
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH2Á Á ÁO2
0.88
0.88
0.95
0.99
2.07
2.55
2.41
2.55
2.5517 (13)
3.4191 (14)
3.2990 (17)
3.5006 (15)
113
172
156
162
N2ÐH2Á Á ÁO11
C3ÐH3Á Á ÁO28i
C27ÐH27AÁ Á ÁO11ii
There are no direction-speci®c interactions between adja-
cent chains; in particular, there are no intermolecular
hydrogen bonds involving the NH fragment, nor are there any
CÐHÁ Á Áꢀ(arene) hydrogen bonds or aromatic ꢀ±ꢀ stacking
interactions.
Symmetry codes: (i) 1 x; 1 y; 1 z; (ii) x; 1 ‡ y; z.
Space group P21/n was uniquely assigned from the systematic
absences. All H atoms were located from difference maps and treated
Experimental
Ê
as riding atoms, with CÐH distances of 0.95 (aromatic) and 0.99 A
Ê
(CH2), and NÐH distances of 0.88 A, and with Uiso(H) values set at
1.2Ueq(C,N).
For the preparation of (I), a suspension of PhNH2 (10 mmol) in cold
NaOH solution (20 ml of 1 mol dm 3) was added to 2-nitro-
phenoxyacetyl chloride (10 mmol) (Minton & Stephen, 1922; Holley
& Holley, 1952). The mixture was stirred for 1 h at 273 K and then
allowed to reach ambient temperature. The precipitate that formed
was collected after 16 h and recrystallized from ethanol, yielding the
title compound [m.p. 394±395 K; literature m.p. 395±397 K (Kirk &
Cohen, 1972)].
Data collection: KappaCCD Server Software (Nonius, 1997); cell
re®nement: DENZO±SMN (Otwinowski & Minor, 1997); data
reduction: DENZO±SMN; program(s) used to solve structure:
OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997);
program(s) used to re®ne structure: OSCAIL and SHELXL97
(Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); soft-
ware used to prepare material for publication: SHELXL97 and
PRPKAPPA (Ferguson, 1999).
Crystal data
3
C14H12N2O4
Mr = 272.26
Monoclinic, P21=n
a = 8.5855 (3) A
Ê
b = 6.6129 (2) A
Dx = 1.447 Mg m
Mo Kꢂ radiation
Cell parameters from 2869
re¯ections
Ê
ꢃ = 3.2±27.6ꢀ
ꢄ = 0.11 mm
T = 120 (2) K
X-ray data were collected at the EPSRC X-ray Crystal-
lographic Service, University of Southampton, England; the
authors thank the staff for all their help and advice. JNL
thanks NCR Self-Service, Dundee, for grants that have
provided computing facilities for this work. JLW thanks CNPq
and FAPERJ for ®nancial support.
1
Ê
c = 22.0221 (8) A
ꢁ = 91.8330 (17)ꢀ
3
Ê
V = 1249.67 (7) A
Z = 4
Block, colourless
0.40 Â 0.30 Â 0.10 mm
Data collection
Nonius KappaCCD diffractometer
' scans, and ! scans with ꢅ offsets
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin = 0.951, Tmax = 0.989
2048 re¯ections with I > 2ꢆ(I)
Rint = 0.028
ꢃ
max = 27.6ꢀ
h = 11 ! 11
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1709). Services for accessing these data are
described at the back of the journal.
k = 8 ! 8
5590 measured re¯ections
2869 independent re¯ections
l = 28 ! 28
ꢁ
Acta Cryst. (2004). C60, o290±o292
Christopher Glidewell et al. C14H12N2O4 o291

organic compounds
Kirk, K. L. & Cohen, L. A. (1972). J. Am. Chem. Soc. 94, 8142±
8147.
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o292 Christopher Glidewell et al.
C14H12N2O4
Acta Cryst. (2004). C60, o290±o292