A chain of edge-fused rings generated by the combination of an N-H·O hydrogen bond and an iodo-nitro interaction in 2-iodobenzaldehyde 4-nitrophenylhydrazone versus disordered and effectively isolated molecules in 2-iodobenzaldehyde 2,4-dinitrophenylhydrazone

Article abstract of DOI:10.1107/S0108270103001379

Molecules of 2-iodobenzaldehyde 4-mitrophenylhydrazone. C₁₃H₁₀IN₃O₂, are effectively planar and are linked by an N-H...O hydrogen both [H...O = 2.04 A, N...O = 2.095 (6) A and N-H...O = 166°] and a two-centre iodonitro interaction [I...O = 3.361 (4) A] into a chain of edge-fused R₃³(18) rings. There are no direction-specific interactions between adjacent chains. Molecules of 2-iodobenzaldehyde 2.4-dinitrophenylhydrazone, C₁₃H₉IN₄O₄, are disordered over two orientations with occupancies of 0.681 (5) and 0.319 (5). In the major orientation, there are no direction-specific intermolecular interactions, while for the minor form, a single C-H...O hydrogen bond generates centrosymmetric dimers.

Full text of DOI:10.1107/S0108270103001379

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
and 2-iodobenzaldehyde 2,4-dinitrophenylhydrazone, (III),
which exhibit radically different patterns of supramolecular
aggregation.
ISSN 0108-2701
A chain of edge-fused rings generated
by the combination of an NÐHÁ Á ÁO
hydrogen bond and an iodo±nitro
interaction in 2-iodobenzaldehyde
4-nitrophenylhydrazone versus
disordered and effectively isolated
molecules in 2-iodobenzaldehyde
2,4-dinitrophenylhydrazone
Christopher Glidewell,a* John N. Low,b Janet M. S.
Skakleb and James L. Wardellc
aSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST,
Scotland, bDepartment of Chemistry, University of Aberdeen, Meston Walk,
c
Â
Old Aberdeen AB24 3UE, Scotland, and Instituto de Quõmica, Departamento
Â
Ã
de Quõmica Inorganica, Universidade Federal do Rio de Janeiro, 21945-970
Molecules of (II) are essentially planar (Fig. 1), as demon-
strated by the torsion angles (Table 1) that de®ne the orien-
tations of the rings relative to the central linked unit. The only
signi®cant deviation from complete planarity is the 5.9 (3)ꢀ
twist of the nitro group out of the plane of the aryl ring C11±
C16.
Rio de Janeiro, RJ, Brazil
Correspondence e-mail: cg@st-andrews.ac.uk
Received 6 January 2003
Accepted 16 January 2003
Online 11 February 2003
The molecules are linked into molecular ladders by the
combination of a single NÐHÁ Á ÁO hydrogen bond (Table 2)
and a single two-centre iodo±nitro interaction. Atom I22 in
the molecule at (x, y, z) forms an iodo±nitro interaction with
atom O42 in the molecule at (x,ꢀ 2 + y, 1 + z)
Molecules of 2-iodobenzaldehyde 4-nitrophenylhydrazone,
C13H10IN3O2, are effectively planar and are linked by an
Ê
NÐHÁ Á ÁO hydrogen bond [HÁ Á ÁO = 2.04 A, NÁ Á ÁO =
ꢀ
Ê
2.905 (6) A and NÐHÁ Á ÁO = 166 ] and a two-centre iodo±
Ê
nitro interaction [IÁ Á ÁO = 3.361 (4) A] into a chain of edge-
[IÁ Á ÁO = 3.361 (4) A, CÐIÁ Á ÁO = 146.5 (2) and IÁ Á ÁOiiÐ
Nii = 146.9 (3)ꢀ; symmetry code: (ii) x, 2 + y, 1 + z], so gener-
ating by translation a C(12) chain (Starbuck et al., 1999)
running parallel to the [021] direction. At the same time,
amino atom N1 at (x, y, z) acts as hydrogen-bond donor to
O41 at (32 x, 1 + y, 21 + z), while N1 at (23 x, 1 + y, 21 + z) in
turn acts as donor to O41 at (x, 2 + y, 1 + z), so producing a
C(8) chain parallel to [021] and generated by the c-glide plane
at x = 34. The combination of these two motifs generates a
molecular ladder (Fig. 2) in which two C(12) iodo±nitro chains
act as the uprights while the NÐHÁ Á ÁO hydrogen bonds act as
the rungs. Alternatively, this substructure may be described as
a chain of edge-fused R33(18) rings.
ii
ii
Ê
fused R33(18) rings. There are no direction-speci®c interactions
between adjacent chains. Molecules of 2-iodobenzaldehyde
2,4-dinitrophenylhydrazone, C13H9IN4O4, are disordered over
two orientations with occupancies of 0.681 (5) and 0.319 (5).
In the major orientation, there are no direction-speci®c
intermolecular interactions, while for the minor form, a single
CÐHÁ Á ÁO hydrogen bond generates centrosymmetric dimers.
Comment
As part of a general study of the interplay of hydrogen bonds,
iodo±nitro interactions and aromatic ꢀ±ꢀ-stacking interac-
tions in aromatic systems containing both iodo and nitro
substituents, we have recently reported the molecular and
supramolecular structures of a range of diaryl species (I) (see
Scheme) containing a variety of spacer units, X, namely
arenesulfonamides (Ia) and (Ib) (Kelly et al., 2002), Schiff base
imines (Ic) (Wardell et al., 2002) and (Id) (Glidewell, Howie et
al., 2002), and two isomeric benzylanilines (Ie) (Glidewell,
Low et al., 2002). Here we report the structure of two analo-
gous compounds containing the ±CH NÐNH± linker unit,
namely 2-iodobenzaldehyde 4-nitrophenylhydrazone, (II),
The [021] ladder lies in the domain 0.47 < x < 1.03. Related
to this ladder by the action of the 21 screw axes is a second
ꢀ
chain, which runs parallel to [021] and lies in the domain
0.03 < x < 0.53. There are no direction-speci®c interactions
between adjacent chains. In particular, there are no CÐHÁ Á ÁO
or CÐHÁ Á Áꢀ(arene) hydrogen bonds and no aromatic ꢀ±ꢀ-
stacking interactions.
Molecules of (III) exhibit orientational disorder (Figs. 3 and
4), with two orientations that have occupancies of 0.681 (5)
o98 # 2003 International Union of Crystallography
DOI: 10.1107/S0108270103001379
Acta Cryst. (2003). C59, o98±o101

organic compounds
Figure 1
The molecular structure of (II), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level.
and 0.319 (5). These orientations are related to one another
approximately via a rotation about the line N1Á Á ÁI22. In both
orientations, the molecules are nearly planar, as typi®ed by the
torsion angles for the major form (Table 3). In contrast to the
supramolecular aggregation in (II), there are neither inter-
molecular NÐHÁ Á ÁO hydrogen bonds nor iodo±nitro inter-
actions in (III). In each orientation there is an intramolecular
NÐHÁ Á ÁO hydrogen bond (Table 4), but for most of the
intermolecular CÐHÁ Á ÁO contacts the HÁ Á ÁO distances are
not signi®cantly shorter than the sum of the van der Waals
radii, and so these bonds are not structurally signi®cant. The
Figure 3
The (a) major and (b) minor orientations of (III), showing the atom-
labelling schemes. Displacement ellipsoids are drawn at the 30%
probability level.
sole exception occurs for the minor orientation, where
centrosymmetrically related molecules are linked into a dimer
via an R22(10) motif (Fig. 5). For the major orientation,
however, the structure must be regarded as being comprised
of isolated molecules.
Figure 2
Part of the crystal structure of (II), showing the formation of a molecular
ladder along [021]. For the sake of clarity, H atoms bonded to C atoms
have been omitted. Atoms marked with an asterisk (*), hash (#), dollar
sign ($) or ampersand (&) are at the symmetry positions (32 x, 1 + y,
12 + z), (x, 2 + y, 1 + z), (23 x, 3 + y, 23 + z) and (23 x, 1 + y, 12 + z),
respectively.
Figure 4
Part of the crystal structure of (III), showing the overlap of the major (full
lines) and minor (broken lines) orientations. For the sake of clarity, H
atoms have been omitted.
ꢁ
Acta Cryst. (2003). C59, o98±o101
Christopher Glidewell et al.
C13H10IN3O2 and C13H9IN4O4 o99

organic compounds
Table 1
Selected torsion angles (ꢀ) for (II).
C11ÐN1ÐN2ÐC27
N1ÐN2ÐC27ÐC21
C12ÐC11ÐN1ÐN2
178.4 (5)
179.1 (5)
178.6 (5)
C22ÐC21ÐC27ÐN2
C13ÐC14ÐN4ÐO41
C13ÐC14ÐN4ÐO42
179.0 (5)
5.8 (8)
174.1 (5)
Figure 5
Table 2
Hydrogen-bonding geometry (A, ) for (II).
Part of the crystal structure of (III), showing the centrosymmetric R22(10)
dimer formed by the minor form. Atoms marked with an asterisk (*) are
at the symmetry position (1 x, 1 y, 2 z).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N1ÐH1Á Á ÁO41i
0.88
2.04
2.905 (6)
166
The occurrence of an iodo±nitro interaction in (II) may be
compared with the absence of such an interaction not only in
(III) but also in those analogues of types (Ic) and (Id) where
the iodo substituent is in a 2-position (Wardell et al., 2002;
Glidewell, Howie et al., 2002). Similarly, the absence of
aromatic ꢀ±ꢀ-stacking interactions from the structures of (II)
and (III) may be compared with the case of 4-nitrobenzyl-
idene-20-iodoaniline, which is of the type (Id) but has the same
disposition of substituents as in (II). In 4-nitrobenzylidene-20-
iodoaniline, such interactions link hydrogen-bonded chains
into sheets. Clearly, the qualitative prediction of which of the
possible weak supramolecular interactions will be signi®cant
in compounds of these general types is far from straightfor-
ward.
3
2
Symmetry codes: (i)
x; 1 ‡ y; 12 ‡ z.
Compound (III)
Crystal data
C13H9IN4O4
Mr = 412.14
Triclinic, P1
a = 7.8890 (5) A
Ê
b = 8.1405 (6) A
Z = 2
Dx = 1.978 Mg m
Mo Kꢁ radiation
3
Ê
Cell parameters from 2924
re¯ections
ꢂ = 1.7±27.4ꢀ
ꢃ = 2.34 mm
T = 120 (2) K
Ê
c = 12.1760 (10) A
1
ꢁ = 83.876 (4)ꢀ
ꢇ = 83.679 (4)ꢀ
ꢈ = 63.151 (3)ꢀ
Plate, orange
0.08 Â 0.06 Â 0.01 mm
3
Ê
V = 691.98 (9) A
Data collection
Nonius KappaCCD diffractometer
' scans, and ! scans with ꢄ offsets
Absorption correction: multi-scan
DENZO±SMN (Otwinowski &
Minor, 1997)
2924 independent re¯ections
2187 re¯ections with I > 2ꢅ(I)
Rint = 0.054
Experimental
For each of (II) and (III), a ®nely powdered mixture of the aldehyde
and the appropriate phenylhydrazine (1:1 molar ratio) was gently
heated on a hot-plate until effervescence ceased. The mixtures were
cooled and crystallized from ethanol.
ꢂmax = 27.4ꢀ
h = 10 ! 9
Tmin = 0.835, Tmax = 0.977
7346 measured re¯ections
k = 10 ! 10
l = 15 ! 15
Re®nement
Compound (II)
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.047
wR(F2) = 0.132
S = 1.07
2924 re¯ections
w = 1/[ꢅ2(F2o) + (0.0694P)2
+ 0.0755P]
Crystal data
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max < 0.001
C13H10IN3O2
Mr = 367.14
Orthorhombic, Pca21
Mo Kꢁ radiation
Cell parameters from 2800
re¯ections
3
Ê
Áꢆmax = 0.84 e A
3
Ê
1.88 e A
243 parameters
H-atom parameters constrained
Áꢆmin
=
ꢂ = 3.4±27.4ꢀ
Ê
a = 24.0858 (11) A
1
Ê
b = 5.0699 (2) A
ꢃ = 2.50 mm
T = 120 (2) K
Ê
c = 10.5080 (4) A
Ê
V = 1283.16 (9) A
3
Table 3
Plate, red
0.32 Â 0.08 Â 0.06 mm
Z = 4
Dx = 1.900 Mg m
Selected torsion angles (ꢀ) for (III).
3
N1ÐN2ÐC27ÐC21
C11ÐN1ÐN2ÐC27
N2ÐN1ÐC11ÐC12
179.6 (7)
171.0 (10)
178.0 (9)
N2ÐC27ÐC21ÐC22
C11ÐC12ÐN12ÐO121
C13ÐC14ÐN14ÐO41
178.2 (7)
6.1 (14)
10.0 (2)
Data collection
Nonius KappaCCD diffractometer
' scans, and ! scans with ꢄ offsets
Absorption correction: multi-scan
DENZO±SMN (Otwinowski &
Minor, 1997)
2800 independent re¯ections
2082 re¯ections with I > 2ꢅ(I)
Rint = 0.063
ꢂ
max = 27.4ꢀ
Table 4
Hydrogen-bonding geometry (A, ) for (III).
h = 31 ! 27
ꢀ
Ê
Tmin = 0.502, Tmax = 0.865
8490 measured re¯ections
k = 6 ! 6
l = 13 ! 13
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Re®nement
N1ÐH1Á Á ÁO121
0.88
0.88
0.95
0.95
0.95
0.95
2.06
2.07
2.58
2.59
2.35
2.60
2.677 (9)
2.716 (13)
3.301 (18)
3.438 (18)
3.21 (3)
126
130
133
149
150
136
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.036
wR(F2) = 0.080
S = 1.02
2800 re¯ections
w = 1/[ꢅ2(F2o) + (0.0298P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max = 0.002
N1ÐH91Á Á ÁO921
C16ÐH16Á Á ÁO122i
C23ÐH23Á Á ÁO41ii
C913ÐH913Á Á ÁO942iii
C916ÐH916Á Á ÁO922iv
3
Ê
Áꢆmax = 1.20 e A
3
Ê
0.47 e A
Áꢆmin
=
3.34 (3)
160 parameters
H-atom parameters constrained
Absolute structure: Flack (1983),
1259 Friedel pairs
Flack parameter = 0.08 (4)
Symmetry codes: (i) 1 ‡ x; y; z; (ii) 1 ‡ x; y 1; z 1; (iii) 1 x; 1 y; 2 z; (iv)
1; y; z.
x
ꢁ
o100 Christopher Glidewell et al.
C13H10IN3O2 and C13H9IN4O4
Acta Cryst. (2003). C59, o98±o101

organic compounds
Compound (II) is orthorhombic and the systematic absences
permitted Pca21 and Pcam (= Pbcm) as possible space groups. Pca21
was chosen and con®rmed by the analysis. Compound (III) is triclinic;
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1609). Services for accessing these data are
described at the back of the journal.
ꢀ
space group P1 was selected and con®rmed by the structure analysis.
In (III), sites N1 and I22 are common to both orientations. In the
minor orientation, the nitrated C911±C916 ring was treated as a rigid
hexagon, and all non-H atoms in this orientation were re®ned
isotropically. DFIX constraints were applied to the nitro group
centred on atom N914. All H atoms were treated as riding atoms, with
References
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Flack, H. D. (1983). Acta Cryst. A39, 876±881.
Glidewell, C., Howie, R. A., Low, J. N., Skakle, J. M. S., Wardell, S. M. S. V. &
Wardell, J. L. (2002). Acta Cryst. B58, 864±876.
Glidewell, C., Low, J. N., Skakle, J. M. S., Wardell, S. M. S. V. & Wardell, J. L.
(2002). Acta Cryst. C58, o487±o490.
Kelly, C. J., Skakle, J. M. S., Wardell, J. L., Wardell, S. M. S. V., Low, J. N. &
Glidewell, C. (2002). Acta Cryst. B58, 94±108.
Nonius (1997). KappaCCD Software. Windows 3.11 Version. Nonius BV,
Delft, The Netherlands.
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.
Ê
CÐH distances of 0.95 A and NÐH distances of 0.88 A.
Ê
For both compounds, data collection: KappaCCD Software
(Nonius, 1997); cell re®nement: DENZO±SMN (Otwinowski &
Minor, 1997); data reduction: DENZO±SMN; program(s) used to
solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to
re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
PLATON (Spek, 2003); software used to prepare material for
publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
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.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
È
Gottingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Starbuck, J., Norman, N. C. & Orpen, A. G. (1999). New J. Chem. 23, 969±
972.
Wardell, J. L., Wardell, S. M. S. V., Skakle, J. M. S., Low, J. N. & Glidewell, C.
(2002). Acta Cryst. C58, o428±o430.
ꢁ
Acta Cryst. (2003). C59, o98±o101
Christopher Glidewell et al. C13H10IN3O2 and C13H9IN4O4 o101