Chains of edge-fused hydrogen-bonded R33(12) rings in N-phenyl-4-nitrophthalimide

Article abstract of DOI:10.1107/S0108270105004245

Molecules of the title compound [systematic name: 5-nitro-1H-isoindole-1, 3(2H)-dione], C₁₄H₈N₂O₄, adopt a conformation in the solid state which renders them chiral, and they are linked by three distinct types o

Full text of DOI:10.1107/S0108270105004245

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
P2 2 2 , only one enantiomorph will be present in each crystal,
1
1 1
providing that inversion twinning is absent. The bond lengths
and angles present no unusual features.
ISSN 0108-2701
Molecules of (I) are linked into chains by the co-operative
action of two CÐHÁ Á ÁO hydrogen bonds, each individually of
only modest strength and each having a nitro O atom as
acceptor, as opposed to the more usual carbonyl O atom. Aryl
atom C7 in the molecule at (x, y, z) acts as hydrogen-bond
donor to nitro atom O51 in the molecule at (x, � 1 + y, z), so
generating by translation a C(6) (Bernstein et al., 1995) chain
running parallel to the [010] direction (Fig. 2). There are four
chains of this type passing through each unit cell and they are
linked in pairs by the second hydrogen bond. Aryl atom C6 at
Chains of edge-fused hydrogen-
bonded R (12) rings in N-phenyl-
3
3
4
-nitrophthalimide
a
b
Christopher Glidewell, * John N. Low, Janet M. S.
b
c
Skakle and James L. Wardell
(
x, y, z) acts as donor towards nitro atom O52 in the molecule
1
a
3
School of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland,
at (1 � x, � + y, � z), so forming a second chain running
1
2
2
b
Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
parallel to [010], this time of C(5) type generated by the 2
screw axis along ( , y, ). The combination of these two
c
AB24 3UE, Scotland, and Instituto de Qu Âõ mica, Departamento de Qu Âõ mica
1
3
2
4
Inorg aà nica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro,
RJ, Brazil
3
simple chain motifs generates a chain of edge-fused R (12)
rings (Fig. 2).
3
Correspondence e-mail: cg@st-andrews.ac.uk
The chains of rings are weakly linked into sheets by a
combination of an aromatic ꢀ±ꢀ stacking interaction and a
dipolar interaction between carbonyl groups. The C3±C8 and
Received 3 February 2005
Accepted 7 February 2005
Online 11 March 2005
Molecules of the title compound [systematic name: 5-nitro-
1H-isoindole-1,3(2H)-dione], C H N O , adopt a conforma-
14 8 2 4
tion in the solid state which renders them chiral, and they are
linked by three distinct types of direction-speci®c inter-
molecular interaction. The molecules are linked by two CÐ
Ê
HÁ Á ÁO hydrogen bonds [HÁ Á ÁO = 2.50 and 2.52 A, CÁ Á ÁO =
Ê
ꢀ
3
chains of edge-fused R (12) rings, which are themselves
.118 (7) and 3.294 (7) A, and CÐHÁ Á ÁO = 123 and 139 ] into
3
3
weakly linked into sheets by a combination of an aromatic ꢀ±ꢀ
stacking interaction and a sheared-parallel carbonyl±carbonyl
interaction.
Figure 1
The molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Comment
As part of a study of the supramolecular arrangements in
N-arylnitrophthalimides, the title compound, (I) (Fig. 1), has
been prepared and its structure determined. The small and
rather simple molecules of (I) are involved in three distinct
types of direction-speci®c intermolecular interaction.
The dihedral angle in (I) between the C11±C16 aryl ring and
ꢀ
the heterocyclic ring is 36.2 (2) . Associated with this inter-
ring twist are two fairly short intramolecular CÐHÁ Á ÁO
contacts (Table 1), which are probably weakly attractive, in
view of the likely positive polarization of the aryl H atoms and
the negative polarization of the carbonyl O atoms. In addition,
the nitro group is not quite coplanar with the adjacent C3±C8
aromatic ring; the dihedral angle between this ring and the C5/
Figure 2
Part of the crystal structure of (I), showing the formation of a chain of
3
R (12) rings along [010]. Atoms marked with an asterisk (*), hash (#),
dollar sign ($) or ampersand (&) are at the symmetry positions (x, � 1 + y,
ꢀ
3
N5/O51/O52 plane is 6.4 (3) . Accordingly, the molecules have
no internal symmetry and are chiral. Thus, in space group
1
2
3
2
1
2
3
2
z), (x, 1 + y, z), (1 � x, � + y, � z) and (1 � x, + y, � z), respectively.
Acta Cryst. (2005). C61, o209±o210
DOI: 10.1107/S0108270105004245
# 2005 International Union of Crystallography o209

organic compounds
1
2
C11±C16 rings in the molecules at (x, y, z) and (2 � x, + y,
Table 1
Hydrogen-bond geometry (A, ).
Ê
ꢀ
3
2
�
z), respectively, are components of the chains of rings
3
1
3
3
generated by the 2 screw axes along ( , y, ) and ( , y, ).
1
2
4
2
4
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
ꢀ
These two rings make a dihedral angle of 12.7 (2) , but their
Ê
ring-centroid separation of 3.770 (3) A and interplanar
Ê
separation of ca 3.6 A suggest a structurally signi®cant inter-
action, the effect of which is to link [010] chains into (001)
sheets. This linking of [010] chains is reinforced by an attrac-
tive dipolar interaction involving the two carbonyl groups. The
C1ÐO1 carbonyl group in the molecule at (x, y, z), which
forms part of the chain along ( , y, ), forms a type III sheared-
parallel interaction (Allen et al., 1998) with the C2ÐO2
i
C6ÐH6Á Á ÁO52
0.95
0.95
2.52
2.50
3.294 (6)
3.118 (7)
139
123
ii
C7ÐH7Á Á ÁO51
1
2
3
2
Symmetry codes: (i) � x ‡ 1; y � ; � z ‡ ; (ii) x; y � 1; z.
Re®nement
2
2
2
o
2
Re®nement on F
2
w = 1/[ꢄ (F
) + (0.0641P)
2
R[F > 2ꢄ(F )] = 0.068
wR(F ) = 0.171
S = 1.09
+ 1.6397P]
where P = (F + 2F )/3
o c
1
3
2
2
2
2
4
(Á/ꢄ)max < 0.001
Ê
� 3
1
554 re¯ections
181 parameters
H-atom parameters constrained
Áꢅmax = 0.39 e A
1
3
Áꢅmin = � 0.25 e AÊ �
3
carbonyl group in the molecule at (2 � x, � + y, � z), part
2
2
3
3
i
of the chain along ( , y, ). The O1Á Á ÁC2 distance is
2
4
i
i
i
Ê
2
are 118.5 (3) and 107.0 (2) , respectively [symmetry code: (i)
.957 (5) A, and the C1ÐO1Á Á ÁC2 and O1Á Á ÁC2 ÐO2 angles
All H atoms were located from difference maps and then treated
Ê
as riding atoms [CÐH = 0.95 A and Uiso(H) = 1.2Ueq(C)]. In the
ꢀ
1
2
3
2
2
� x, � + y, � z]. It may be noted here that, although the
absence of signi®cant anomalous dispersion, the Flack parameter
(Flack, 1983) was inconclusive (Flack & Bernardinelli, 2000). Hence,
the Friedel-equivalent re¯ections were merged prior to the ®nal
re®nement and it was not possible to determine the absolute
con®guration of the molecules in the crystal used for the data
collection. However, this con®guration has no chemical signi®cance.
Data collection: COLLECT (Hooft, 1999); cell re®nement and
carbonyl O atoms participate in both of the short intra-
molecular contacts and in the intermolecular dipolar inter-
actions, they play no part at all in the intermolecular hydrogen
bonding.
Two (010) sheets pass through each unit cell, generated by
1
3
21
speci®c interactions between adjacent sheets.
screw axes at z = and z = , but there are no direction-
4 4
data reduction: DENZO (Otwinowski
& Minor, 1997) and
COLLECT; structure solution: OSCAIL (McArdle, 2003) and
SHELXS97 (Sheldrick, 1997); structure re®nement: OSCAIL and
SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,
It is of interest to compare brie¯y the supramolecular
structure of (I) with those of isomeric compounds having the
nitro substituent in the N-phenyl ring. In N-(2-nitro-
2003); software used to prepare material for publication: SHELXL97
and PRPKAPPA (Ferguson, 1999).
phenyl)phthalimide (Voliotis et al., 1984), pairs of molecules
2
are linked by a single CÐHÁ Á ÁO hydrogen bond into R (14)
2
dimers, which are themselves linked into ꢀ-stacked chains,
while in N-(3-nitrophenyl)phthalimide (Glidewell et al., 2004),
the molecules are linked into a three-dimensional framework
utilizing four independent CÐHÁ Á ÁO hydrogen bonds.
The X-ray data were collected at the EPSRC X-ray Crys-
tallographic Service, University of Southampton, England; the
authors thank the staff for all their help and advice. JNL
thanks NCR Self-Service, Dundee, for grants which have
provided computing facilities for this work. JLW thanks CNPq
and FAPERJ for ®nancial support.
Experimental
2
Awell ground mixture of PhNH (0.19 g, 2 mmol) and 4-nitrophthalic
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1814). Services for accessing these data are
described at the back of the journal.
anhydride (0.38 g, 2 mmol) was carefully heated at 473 K until
effervescence (water evolution) ceased. To the cooled solid residue
was added chloroform (10 ml) and activated charcoal. The resulting
mixture was heated to re¯ux, ®ltered, and the ®ltrate evaporated. The
residue was recrystallized from ethanol to provide compound (I).
References
Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta
Cryst. B54, 320±329.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Flack, H. D. (1983). Acta Cryst. A39, 876±881.
Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143±1148.
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2004). Acta Cryst.
C60, o24±o27.
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography
Centre, Chemistry Department, NUI Galway, Ireland.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307±326. New York: Academic Press.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
G oÈ ttingen, Germany.
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of G oÈ ttingen,
Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Crystal data
C
14
H
8
N
2
O
4
Mo Kꢁ radiation
Cell parameters from 1554
re¯ections
r
M = 268.22
Orthorhombic, P2 2 2
1
1
1
Ê
a = 11.9288 (6) A
ꢀ
ꢂ = 2.9±27.6
ꢃ = 0.12 mm
T = 120 (2) K
Ê
b = 7.0604 (2) A
� 1
Ê
c = 13.8337 (7) A
Ê
V = 1165.10 (9) A
Z = 4
3
Needle, yellow
0.12 Â 0.04 Â 0.03 mm
�
3
D
x
= 1.529 Mg m
Data collection
Nonius KappaCCD area-detector
diffractometer
1554 independent re¯ections
1318 re¯ections with I > 2ꢄ(I)
'
and ! scans
Absorption correction: multi-scan
SADABS; Sheldrick, 2003)
min = 0.963, Tmax = 0.997
3 798 measured re¯ections
Rint = 0.070
ꢀ
ꢂ
max = 27.6
(
T
h = � 15 ! 13
k = � 9 ! 9
1
l = � 17 ! 17
Voliotis, S., Arrieta, J. M. & Germain, G. (1984). Acta Cryst. C40, 1946±1948.
ꢁ
o210 Glidewell et al.
C H N
14 8 2
O
4
Acta Cryst. (2005). C61, o209±o210