2,6-diiodo-4-nitrophenol, 2,6-diiodo-4-nitrophenyl acetate and 2,6-diiodo-4-nitroanisole: Interplay of hydrogen bonds, iodo-nitro interactions and aromatic π-π-stacking interactions to give supramolecular structures in one, two and three dimensions

Article abstract of DOI:10.1107/S0108270102010776

In 2,6-diiodo-4-nitrophenol, C₆H₃I₂NO₃, the molecules are linked, by an O-H...O hydrogen bond and two iodo-nitro interactions, into sheets, which are further linked into a three-dimensional framework by aromatic π-π-stacking interactions. The molecules of 2,6-diiodo-4-nitrophenyl acetate, C₈H₅I₂NO₄, lie across a mirror plane in space group Pnma, with the acetyl group on the mirror, and they are linked by a single iodo-nitro interaction to form isolated sheets. The molecules of 2,6-diiodo-4-nitroanisole, C₇H₅I₂NO₃, are linked into isolated chains by a single two-centre iodo-nitro interaction.

Full text of DOI:10.1107/S0108270102010776

organic compounds
Acta Crystallographica Section C
Crystal Structure
retaining the other potential intermolecular interactions, in
that (I) has an OH group in place of the NH group in simple
2
Communications
anilines, allowing the molecule to act as only a single donor in
such bonds, while (II) and (III) have no scope at all for the
formation of hard hydrogen bonds.
ISSN 0108-2701
2
4
4
,6-Diiodo-4-nitrophenol, 2,6-diiodo-
-nitrophenyl acetate and 2,6-diiodo-
-nitroanisole: interplay of hydrogen
bonds, iodo±nitro interactions and
aromatic p±p-stacking interactions to
give supramolecular structures in one, hydrogen bonds and two independent iodo±nitro interactions
two and three dimensions
In compound (I) (Fig. 1), a combination of OÐHÁ Á ÁO
links the molecules into sheets, and these sheets are weakly
linked by aromatic ꢀ±ꢀ-stacking interactions to form a
continuous three-dimensional structure. The phenolic atom
O1 acts as a hydrogen-bond donor to nitro atom O41 at (1 + x,
y � 1, z) (Table 2), so generating by translation a C(8) chain
(Bernstein et al., 1995) running parallel to the [110] direction.
Chains of this type are linked into sheets by the iodo±nitro
interactions, which involve both I atoms and both nitro O
atoms. Atoms I2 and I6 participate in iodo±nitro interactions
a
a
Simon J. Garden, Fernanda R. da Cunha, James L.
b
c
c
Wardell, Janet M. S. Skakle, John N. Low ² and
d
Christopher Glidewell *
a
Instituto de Qu Âõ mica, Departamento de Qu Âõ mica Org aà nica, Universidade Federal do
b
Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, Instituto de Qu Âõ mica,
Departamento de Qu Âõ mica Inorg aà nica, Universidade Federal do Rio de Janeiro,
i
c
with nitro atoms O42 and O41, respectively [I2Á Á ÁO42
2
1945-970 Rio de Janeiro, RJ, Brazil, Department of Chemistry, University of
d
Ê
i
ꢀ
ii
Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and School of
Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
3.326 (4) A and C2ÐI2Á Á ÁO42 152.2 (2) , and I6Á Á ÁO41
ii
ꢀ
Ê
3
1
.552 (4) A and C6ÐI6Á Á ÁO41 157.9 (2) ; symmetry codes: (i)
� x, 1 � y, � z; (ii) � x, 1 � y, 2 � z], so generating
2
2
1
2
centrosymmetric R (12) rings centred at ( ,0,0) and (0,0,1),
Received 29 May 2002
Accepted 17 June 2002
Online 12 July 2002
respectively. The combination of these two motifs generates a
chain of fused rings running parallel to the [102] direction,
while the combination of this chain with the hydrogen-bonded
chain along [110] generates a (221) sheet in which there are
four distinct types of ring, all centrosymmetric (Fig. 2).
The aromatic ring of (I) forms a close ꢀÁ Á Áꢀ contact with
that at (1 � x, 1 � y, 1 � z) (Fig. 3); the interplanar spacing
In 2,6-diiodo-4-nitrophenol, C H I NO , the molecules are
3
6
3 2
linked, by an OÐHÁ Á ÁO hydrogen bond and two iodo±nitro
interactions, into sheets, which are further linked into a three-
dimensional framework by aromatic ꢀ±ꢀ-stacking interac-
tions. The molecules of 2,6-diiodo-4-nitrophenyl acetate,
Ê
between parallel rings is 3.379 (4) A, the centroid separation is
C H I NO , lie across a mirror plane in space group Pnma,
5 2
Ê
Ê
8
4
3.493 (4) A and the centroid offset is 0.886 (4) A. In this
manner, each (221) sheet (Fig. 2) is linked to the two adjacent
sheets, so generating a continuous framework in three
dimensions.
with the acetyl group on the mirror, and they are linked by a
single iodo±nitro interaction to form isolated sheets. The
molecules of 2,6-diiodo-4-nitroanisole, C H I NO , are linked
7
5 2
3
into isolated chains by a single two-centre iodo±nitro
interaction.
Comment
We have recently reported the molecular and supramolecular
structures of several iodonitroanilines, unsubstituted at N
(
Garden et al., 2002). In these compounds, the supramolecular
aggregation is dominated by a combination of NÐHÁ Á ÁO
hydrogen bonds, iodo±nitro interactions and aromatic ꢀ±ꢀ-
stacking interactions, to give either two- or three-dimensional
structures. The title compounds, 2,6-diiodo-4-nitrophenol, (I),
2,6-diiodo-4-nitrophenyl acetate, (II), and 2,6-diiodo-4-nitro-
anisole, (III), have been designed to reduce the scope for
formation of hard (Braga et al., 1995) hydrogen bonds, while
Figure 1
The molecule of (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.
² Postal address: School of Engineering, University of Dundee, Dundee
DD1 4HN, Scotland.
Acta Cryst. (2002). C58, o463±o466
DOI: 10.1107/S0108270102010776
# 2002 International Union of Crystallography o463

organic compounds
Molecules of compound (II) lie across the mirror planes in
space group Pnma (Fig. 4). The non-H atoms of the acetate
group all lie on the mirror plane (chosen for the sake of
exhibits neither CÐHÁ Á ÁO hydrogen bonds nor aromatic ꢀ±ꢀ-
stacking interactions. Instead, the single short iodo±nitro
interaction generates a simple and elegant sheet structure
(Fig. 5).
1
convenience as that at y = for the reference molecule), so
4
that the plane of the acetate group is orthogonal to the
aromatic ring. The methyl group was modelled using six
H-atom sites, each with occupancy 0.5. The crystal structure
Each of the two symmetry-related I atoms in (II) partici-
pates in a two-centre iodo±nitro interaction with the O4 atoms
1
1
1
1
1
at ( � x, 1 � y, z � ) and ( � x, y � , z � ), respectively,
2
2
2
2
2
Ê
ꢀ
with I2Á Á ÁO4 3.323 (3) A and CÐIÁ Á ÁO4 140.8 (2) . Propaga-
tion of these interactions produces two C(6) chain motifs
running parallel to the [001] direction and generated by the 2
screw axes along ( , ,z) and ( ,0,z). The combination of these
two symmetry-related motifs and their propagation by the
1
1
4
1
2
1
4
space group generates a (100) sheet in the form of a (4,4) net
4
(Batten & Robson, 1998) built from a single type of R (20)
4
Figure 4
The molecule of (II), 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. Atoms with the suf®x A are at the
symmetry position (x, 1 � y, z). For the sake of clarity, only one set of H
atoms bonded to C12 is shown.
Figure 2
Part of the crystal structure of (I), showing the formation of a (110) sheet
containing four distinct centrosymmetric rings. For the sake of clarity, H
atoms bonded to C atoms have been omitted. Atoms marked with an
asterisk (*), hash (#), dollar sign ($) or ampersand (&) are at the
symmetry positions (1 + x, y � 1, z), (1 � x, 1 � y, � z), (� x, 1 � y, 2 � z)
and (x � 1, 1 + y, z), respectively.
Figure 5
Part of the crystal structure of (II), showing the formation of a (100) sheet
4
of R (20) rings. For the sake of clarity, H atoms bonded to C atoms have
been omitted. Atoms marked with a plus sign (+), asterisk (*), hash (#),
4
Figure 3
1
Part of the crystal structure of (I), showing the ꢀ±ꢀ-stacking interaction.
dollar sign ($) or ampersand (&) are at the symmetry positions (x, � y,
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
Atoms marked with an asterisk (*) are at the symmetry position (1 � x,
z), ( � x, 1 � y, z � ), ( � x, y � , z � ), ( � x, y � , + z) and ( � x,
2
1
2
1
� y, 1 � z).
1 � y, + z), respectively.
ꢁ
o464 Simon J. Garden et al.
6 3
C H I
2
NO
3
8 5
, C H I
2
NO
4
7 5
and C H I
2
NO
3
Acta Cryst. (2002). C58, o463±o466

organic compounds
iv
ꢀ
Ê
ring. The central space in each ring is occupied by an acetate
group.
2.992 (3) A and C2ÐI2Á Á ÁO42 171.3 (2) ; symmetry code:
1
1
1
2
(iv) 2 + x, 2 � y, z � ], and propagation of this interaction
In compound (III) (Fig. 6), neither CÐHÁ Á ÁO hydrogen
bonds nor aromatic ꢀ±ꢀ-stacking interactions are present in
the crystal structure. The molecules are linked into chains by
an iodo±nitro interaction involving only one of the two I
atoms and only one of the nitro O atoms. Atom I2 in the
molecule at (x, y, z) forms a very short IÁ Á ÁO contact with nitro
leads to the formation of a chain running parallel to the [101]
1
direction, generated by the n glide plane at y = (Fig. 7).
4
The intermolecular distances and angles in compounds (I)±
(III) present no unusual features. In each compound, the nitro
group is almost coplanar with the adjacent aryl ring (Tables 1,
3 and 4).
1
2
1
2
1
2
iv
atom O42 in the molecule at ( + x, � y, z � ) [I2Á Á ÁO42
Experimental
Compound (I) was obtained by reaction of 4-nitrophenol with
2
K[ICl ] in aqueous solution (Garden et al., 2001). Compounds (II)
and (III) were obtained from (I) by acetylation using acetic anhy-
dride and methylation using dimethyl sulfate, respectively. Crystals of
(
I)±(III) suitable for single-crystal X-ray diffraction were grown by
slow evaporation of solutions in ethanol [m.p. 439±441 K for (I), 409±
11 K for (II) and 418±419 K for (III)].
4
Compound (I)
Crystal data
C
M
6
H
3
I
2
NO
= 390.89
Triclinic, P1
3
Z = 2
= 3.001 Mg m
Mo Kꢁ radiation
�
3
r
D
x
Ê
Ê
a = 7.9749 (2) A
b = 8.0952 (3) A
Ê
c = 8.1395 (3) A
Cell parameters from 1850
re¯ections
Figure 6
ꢀ
ꢄ = 2.9±27.4
The molecule of (III), 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.
ꢀ
� 1
ꢁ
= 69.3082 (18)
ꢀ
ꢅ = 7.24 mm
T = 120 (2) K
ꢂ = 66.657 (2)
ꢃ = 67.3547 (15)
Ê
V = 432.59 (3) A
ꢀ
3
Block, yellow
0.15 Â 0.10 Â 0.05 mm
Data collection
Nonius KappaCCD area-detector
diffractometer
1850 independent re¯ections
1735 re¯ections with I > 2ꢇ(I)
'
scans, and ! scans with ꢆ offsets
Absorption correction: multi-scan
DENZO-SMN; Otwinowski &
Minor, 1997)
min = 0.297, Tmax = 0.700
596 measured re¯ections
Rint = 0.091
ꢀ
ꢄ
max = 27.4
(
h = � 10 ! 10
k = � 10 ! 10
l = � 10 ! 10
T
4
Re®nement
2
2
2
2
Re®nement on F
2
o
w = 1/[ꢇ (F ) + (0.0584P)
2
R[F > 2ꢇ(F )] = 0.032
wR(F ) = 0.115
S = 1.17
+ 0.3136P]
where P = (F
(Á/ꢇ)max < 0.001
Áꢈmax = 1.35 e A
Áꢈmin = � 1.57 e AÊ
2
2
2
c
o
+ 2F
)/3
Ê
� 3
1
1
850 re¯ections
10 parameters
� 3
H-atom parameters constrained
Table 1
Selected torsion angles ( ) for (I).
ꢀ
C3ÐC4ÐN4ÐO41
� 178.5 (6)
C3ÐC4ÐN4ÐO42
1.1 (8)
Table 2
Hydrogen-bonding geometry (A, ) for (I).
Ê
ꢀ
Figure 7
Part of the crystal structure of (III), showing the formation of a chain
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
along [101]. Atoms marked with an asterisk (*) or hash (#) are at the
1
i
O1ÐH1Á Á ÁO41
Symmetry code: (i) 1 ‡ x; y � 1; z.
0.84
2.20
2.808 (6)
129
1
1
1
2
1
2
1
2
symmetry positions (x � , 2 � y, 2 + z) and ( + x, � y, z � ),
2
respectively.
ꢁ
Acta Cryst. (2002). C58, o463±o466
Simon J. Garden et al.
6
C H
3
I
2 3 8
NO , C H
5
I
2
NO
4
7
and C H
5
I
2
NO
3
o465

organic compounds
Compound (II)
Table 4
Selected torsion angles ( ) for (III).
ꢀ
Crystal data
C3ÐC4ÐN4ÐO41
C3ÐC4ÐN4ÐO42
� 7.4 (5)
C2ÐC1ÐO1ÐC11
C6ÐC1ÐO1ÐC11
89.7 (5)
� 94.7 (5)
C
8
H
5
I
2
NO
4
Mo Kꢁ radiation
Cell parameters from 2206
re¯ections
173.0 (4)
M
Orthorhombic, Pnma
Ê
a = 8.0608 (9) A
b = 12.4501 (14) A
c = 11.6790 (13) A
Ê
V = 1172.1 (2) A
Z = 4
r
= 432.93
ꢀ
ꢄ = 2.4±32.6
ꢅ = 5.36 mm
T = 292 (2) K
Ê
Ê
� 1
3
Block, colourless
0.50 Â 0.23 Â 0.12 mm
Compound (I) is triclinic; space group P1 was selected and
con®rmed by the analysis. For compound (II), the systematic
�
3
D
x
= 2.453 Mg m
1 1
absences permitted Pnma and Pn2 a (= Pna2 ) as possible space
groups; Pnma was selected and con®rmed by the structure analysis.
For compound (III), the systematic absences permitted C2/c and Cc
as possible space groups; C2/c was selected and con®rmed by the
Data collection
Bruker SMART 1000 CCD area-
detector diffractometer
2206 independent re¯ections
1555 re¯ections with I > 2ꢇ(I)
'
and ! scans
Absorption correction: multi-scan
SADABS; Bruker, 1999)
min = 0.258, Tmax = 0.528
1 456 measured re¯ections
R
int = 0.044
analysis. All H atoms were located from difference maps and were
treated as riding atoms, with OÐH distances of 0.84 AÊ and CÐH
Ê
distances in the range 0.93±0.98 A.
ꢀ
ꢄ
max = 32.6
(
T
h = � 12 ! 12
k = � 17 ! 18
l = � 17 ! 15
For compounds (I) and (III), data collection: KappaCCD Server
Software (Nonius, 1997); cell re®nement: DENZO±SMN (Otwi-
nowski & Minor, 1997); data reduction: DENZO±SMN. For
compound (II), data collection: SMART (Bruker, 1999); cell re®ne-
ment: SAINT (Bruker, 1999); data reduction: SAINT. For all three
compounds, program(s) used to solve structure: SHELXS97 (Shel-
drick, 1997); program(s) used to re®ne structure: SHELXL97
(Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); soft-
ware used to prepare material for publication: SHELXL97 and
PRPKAPPA (Ferguson, 1999).
1
Re®nement
2
2
2
2
Re®nement on F
2
R[F > 2ꢇ(F )] = 0.041
wR(F ) = 0.112
S = 1.04
o
w = 1/[ꢇ (F ) + (0.0513P)
2
+ 0.8851P]
where P = (F
2
2
2
c
o
+ 2F
)/3
(Á/ꢇ)max < 0.001
Áꢈmax = 1.20 e A
Áꢈmin = � 0.41 e A
Extinction correction: SHELXL97
Sheldrick, 1997)
Extinction coef®cient: 0.0321 (13)
Ê
� 3
2
8
206 re¯ections
1 parameters
Ê
� 3
H-atom parameters constrained
(
The X-ray data for (I) and (III) were collected at the
EPSRC X-ray Crystallographic Service, University of South-
ampton, England; the authors thank the staff for all their help
and advice. The data for (II) were collected at the University
of Aberdeen, Scotland. JNL thanks NCR Self-Service,
Dundee, for grants which have provided computing facilities
for this work. SJG, FRC and JLW thank CNPq and FAPERJ
for ®nancial support.
Table 3
Selected torsion angles ( ) for (II).
ꢀ
C3ÐC4ÐN4ÐO4
C3ÐC4ÐN4ÐO4
1.6 (6)
179.9 (4)
C2ÐC1ÐO1ÐC11
� 92.6 (3)
i
1
2
Symmetry code: (i) x; � y; z.
Compound (III)
Crystal data
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: TR1033). Services for accessing these data are
described at the back of the journal.
�
3
C
H I
7 5 2
NO
3
D
x
= 2.640 Mg m
M
r
= 404.92
Mo Kꢁ radiation
Monoclinic, C2=c
a = 15.2372 (3) A
Ê
b = 16.2672 (4) A
Cell parameters from 2312
re¯ections
Ê
ꢀ
ꢄ = 2.9±27.5
ꢅ = 6.15 mm
T = 120 (2) K
Ê
c = 8.3262 (2) A
� 1
References
ꢀ
Ê
ꢂ = 99.2039 (15)
V = 2037.22 (8) A
Z = 8
3
Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460±1494.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Block, yellow
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Bruker (1999). SADABS (Version 2.03), SAINT (Version 6.02a) and SMART
Data collection
Nonius KappaCCD area-detector
diffractometer
2312 independent re¯ections
2068 re¯ections with I > 2ꢇ(I)
(
Version 5). Bruker AXS Inc., Madison, Wisconsin, USA.
'
scans, and ! scans with ꢆ offsets
Absorption correction: multi-scan
DENZO±SMN; Otwinowski &
Minor, 1997)
min = 0.530, Tmax = 0.829
397 measured re¯ections
Rint = 0.056
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Garden, S. J., Fontes, S. P., Wardell. J. L., Skakle, J. M. S., Low, J. N. &
Glidewell, C. (2002). Acta Cryst B58. In the press.
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Lima, E. L. S. (2001). Tetrahedron Lett. 42, 2089±2092.
Nonius (1997). KappaCCD Server 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.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
G oÈ ttingen, Germany.
ꢀ
ꢄ
max = 27.5
(
h = � 19 ! 19
k = � 21 ! 18
l = � 10 ! 10
T
7
Re®nement
2
Re®nement on F
2
H-atom parameters constrained
2
2
2
2
R[F > 2ꢇ(F )] = 0.033
wR(F ) = 0.077
S = 1.07
w = 1/[ꢇ (F
where P = (F
(Á/ꢇ)max < 0.001
o
) + (0.0371P) ]
2
2 2
+ 2F
c
o
)/3
Ê
� 3
2
1
312 re¯ections
19 parameters
Áꢈmax = 1.42 e A
Áꢈmin = � 1.65 e AÊ
Spek, A. L. (2002). PLATON. Version of April 2002. University of Utrecht,
The Netherlands.
� 3
ꢁ
o466 Simon J. Garden et al.
6 3
C H I
2
NO
3
8 5
, C H I
2
NO
4
7 5
and C H I
2
NO
3
Acta Cryst. (2002). C58, o463±o466