2-Cyano-4-iodo-acetanilide: A hydrogen-bonded chain of R 2 2(12) and R22(14) rings

Article abstract of DOI:10.1107/S0108270107026492

The mol-ecules of 2-cyano-4-iodo-acetanilide, C9H7IN2O, are linked by N - H...N and C - H...O hydrogen bonds into chains of alternating R 2 ²(12) and R 2 ²(14) rings. International Union of Crystallography 2007.

Full text of DOI:10.1107/S0108270107026492

organic compounds
Acta Crystallographica Section C
Crystal Structure
hydrogen bonds. The remaining bond lengths and angles show
no unusual features.
Communications
Two intermolecular hydrogen bonds link the molecules of
(I) into chains of fused rings. Atoms N1 and C5 in the mole-
cule at (x, y, z) act as hydrogen-bond donors, respectively, to
atoms N2 in the molecule at (2 � x, 1 � y, 1 � z) and O1 in the
molecule at (� x, 2 � y, 1 � z). Propagation by inversion of
these two interactions generates a chain of rings running
ISSN 0108-2701
2
-Cyano-4-iodoacetanilide: a
2
2
hydrogen-bonded chain of R (12)
2
parallel to the [210] direction, with centrosymmetric R (12)
rings (Bernstein et al., 1995) containing NÐHÁ Á ÁN hydrogen
2
2
2
and R (14) rings
1
1
bonds and centred at (2n + 1, 2 � n, ) (where n represents
2
2
2
a
b
zero or an integer) alternating with centrosymmetric R (14)
rings containing CÐHÁ Á ÁO hydrogen bonds and centred at
Simon J. Garden, C Âõ ntia de A. Cust o dio, James L.
a
c
d
Wardell, John N. Low and Christopher Glidewell *
1
2
(
2n, 1 � n, ) (where n represents zero or an integer) (Fig. 2).
a
Universidade Federal do Rio de Janeiro, Instituto de Qu Âõ mica, Cidade Universit a ria,
The structure of the related compound (II) has recently
b
CT, Bloco A, Ilha do Fund Äa o, Rio de Janeiro, RJ, CEP 21941-909, Brazil, Instituto de
been reported (Arslan et al., 2005). The structure was
described as forming sheets parallel to (100) generated by a
combination of NÐHÁ Á ÁN and CÐHÁ Á ÁO hydrogen bonds.
The formation of a two-dimensional supramolecular structure
Engenharia Nuclear, Via Cinco, Cidade Universit a ria, Ilha do Fund Äa o, Rio de Janeiro,
c
RJ, CEP 21945-970, Brazil, Department of Chemistry, University of Aberdeen,
d
Meston Walk, Old Aberdeen AB24 3UE, Scotland, and School of Chemistry,
University of St Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
in the space group P2 2 2 is somewhat unexpected, and re-
1 1 1
analysis of the published structure shows that the hydrogen-
bonded structure of (II) is, in fact, three-dimensional. The NÐ
HÁ Á ÁN and CÐHÁ Á ÁO hydrogen bonds, acting individually,
form chains running parallel to the [100] and [010] directions,
Received 30 May 2007
Accepted 31 May 2007
Online 14 June 2007
of C(6) and C(8) types, respectively, while in combination they
2
The molecules of 2-cyano-4-iodoacetanilide, C H IN O, are
7
9
2
form a C (10) chain running parallel to the [001] direction, so
2
linked by NÐHÁ Á ÁN and CÐHÁ Á ÁO hydrogen bonds into
2
2
2
2
completing the three-dimensional framework. The original
report on (II) (Arslan et al., 2005) showed the structure in
chains of alternating R (12) and R (14) rings.
projection along [100], and the published packing diagram
2
appears to show the formation of R (12) rings containing pairs
2
Comment
of NÐHÁ Á ÁN hydrogen bonds, when in fact this hydrogen
bond forms C(6) chains along the direction of the projection
and thus normal to the plane of the supposed hydrogen-
bonded sheet.
Although the iodine substituent in (I) plays no direct role in
the supramolecular aggregation, its presence leads to an
We report here the molecular and supramolecular structures
of 2-cyano-4-iodoacetanilide, (I) (Fig. 1), and compare the
structure of (I) with that of the simpler analogue 2-cyano-
acetanilide, (II), for which we have re-interpreted the recently
published structure (Arslan et al., 2005). The present study is a
continuation of our extended programme on the supra-
molecular structures of substituted iodoaniline derivatives
(
Ferguson et al., 2005; Garden et al., 2002, 2004, 2005, 2006;
Garden, Glidewell et al., 2001; Glidewell et al., 2004; McWil-
liam et al., 2001).
In (I), the C6ÐC1ÐN1, C1ÐN1ÐC11 and N1ÐC11ÐO1
ꢀ
angles are all signi®cantly larger than 120 (Table 1),
suggesting that the short intramolecular H6Á Á ÁO1 contact
(
Table 2) may be repulsive rather than attractive. Despite this,
the molecule of (I) is almost planar, as indicated by the leading
torsion angles, and it is thus possible that the overall molecular
conformation results from a balance between repulsive
intramolecular contacts and attractive intermolecular
Figure 1
The molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
o408 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270107026492
Acta Cryst. (2007). C63, o408±o410

organic compounds
entirely different supramolecular structure in (I) as compared
with (II), even though the structures of (I) and (II) are each
built from the combination of one NÐHÁ Á ÁN hydrogen bond
and one CÐHÁ Á ÁO hydrogen bond.
Data collection
Bruker±Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
7314 measured re¯ections
2160 independent re¯ections
2047 re¯ections with I > 2ꢅ(I)
(
T
SADABS; Sheldrick, 2003)
min = 0.503, Tmax = 0.937
Rint = 0.038
Re®nement
2
2
R[F > 2ꢅ(F )] = 0.027
wR(F ) = 0.058
119 parameters
H-atom parameters constrained
2
Ê
� 3
Áꢆmax = 0.56 e A
S = 1.04
2160 re¯ections
Áꢆmin = � 0.49 e AÊ
� 3
Table 1
Selected bond angles ( ).
ꢀ
C6ÐC1ÐN1
C1ÐN1ÐC11
122.5 (3)
126.8 (2)
N1ÐC11ÐO1
122.6 (3)
Table 2
Hydrogen-bond geometry (A, ).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Figure 2
A stereoview of part of the crystal structure of (I), showing a chain of
i
N1ÐH1Á Á ÁN2
C5ÐH5Á Á ÁO1
C6ÐH6Á Á ÁO1
0.86
0.95
0.95
2.54
2.38
2.24
3.309 (4)
3.214 (4)
2.815 (4)
149
147
118
ii
2
2
alternating R (12) and R (14) rings running parallel to [210]. For the sake
of clarity, H atoms not involved in the motifs shown have been omitted.
2
2
Symmetry codes: (i) � x ‡ 2; � y ‡ 1; � z ‡ 1; (ii) � x; � y ‡ 2; � z ‡ 1.
Experimental
Crystals of (I) are triclinic; the space group P1 was selected and
con®rmed by the subsequent structure analysis. All H atoms were
located in difference maps and then treated as riding atoms in
geometrically idealized positions, with CÐH distances of 0.95
Compound (I) was prepared by the acetylation of 2-amino-5-iodo-
benzonitrile, prepared as follows. K(ICl ) (Garden, Torres et al., 2001)
2
�
3
3 ml of a 2 mol dm solution in water) was added to a methanol
(
Ê
aromatic) or 0.98 A (methyl), NÐH distances of 0.86 A and
Ê
(
solution (15 ml) of 2-aminobenzonitrile (0.510 g, 5.0 mmol). The
reaction mixture was stirred at room temperature. After 2 h, the
product had precipitated and the benzonitrile substrate had been
completely consumed. The reaction mixture was diluted with water
Uiso(H) = kUeq(C,N), where k = 1.5 for the methyl group and k = 1.2
for all other H atoms.
Data collection: COLLECT (Nonius, 1999); cell re®nement:
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduc-
tion: DENZO and COLLECT; program(s) used to solve structure:
OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997);
program(s) used to re®ne structure: OSCAIL and SHELXL97
(
(
50 ml) and the product was collected by ®ltration and dried in air
yield 93%). Recrystallization from aqueous ethanol (97:3 v/v) gave
pale-brown plates [m.p. 356±357 K; literature (Harris et al., 1992)
3
7
1
1
2
58 K]. NMR (CDCl
3
): ꢀ
H
6.20 (2H, s, NH
2
), 6.62 (1H, d, J = 8.8 Hz),
: 74.9, 96.0,
(Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); soft-
.52 (1H, dd, J = 8.8 and 2.0 Hz), 7.65 (1H, d, J = 2.0 Hz); ꢀ
C
�
1
ware used to prepare material for publication: SHELXL97 and
PRPKAPPA (Ferguson, 1999).
16.8, 117.8, 139.7, 142.2, 151.2. IR (KBr disk, cm ): 3456, 3359, 2224,
643, 1552, 1483, 1402, 1155, 899, 820. The product (0.500 g,
.0 mmol) was treated with acetic anhydride (1 ml) and acetic acid
(2 ml). The reaction mixture was warmed gently for a few minutes
then hydrolyzed with water (20 ml). The product, (I), was collected
by ®ltration and recrystallized from aqueous ethanol (97:3 v/v) (yield
X-ray data were collected at the EPSRC National Crystal-
lography Service, University of Southampton, England. The
authors thank the staff for all their help and advice. SJG
thanks CNPq, and JLW thanks CNPq and FAPERJ for
3 H 3
79%, m.p. 449±451 K). NMR (CDCl ): ꢀ 2.27 (3H, s, CH ), 7.69 (1H,
br, s, NH), 7.85 (1H, dd, J = 10 and 1.9 Hz, H-5), 7.87 (1H, d, J =
®nancial support.
1
1
1
C
.9 Hz, H-3), 8.19 (1H, d, J = 10 Hz, H-6); ꢀ 24.4, 85.5, 103.2, 114.5,
22.4, 139.7, 139.9, 142.7, 168.2. IR (KBr disk, cm ): 3344, 3054, 2225,
689, 1577, 1516, 1383, 1369, 1295, 1258, 1182, 1122, 884, 842.
�
1
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3136). Services for accessing these data are
described at the back of the journal.
Crystal data
IN
= 286.07
Triclinic, P1
ꢀ
ꢃ = 90.926 (2)
V = 476.51 (3) A
Z = 2
C
M
9
H
7
2
O
Ê
3
r
References
Ê
a = 4.6657 (2) A
Mo Kꢁ radiation
Ê
b = 9.4172 (4) A
� 1
ꢄ = 3.32 mm
T = 120 (2) K
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Ê
c = 11.6841 (4) A
ꢀ
ꢁ
= 109.7520 (17)
ꢀ
0.24 Â 0.06 Â 0.02 mm
ꢂ = 98.598 (2)
ꢁ
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Garden et al.
C H
9 7
2
IN O
o409

organic compounds
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ꢁ
o410 Garden et al.
9 7 2
C H IN O
Acta Cryst. (2007). C63, o408±o410