2-Iodo-6-methoxy-4-nitro­aniline: tripartite ribbons built from N—H⋯O hydrogen bonds and iodo–nitro interactions are π-stacked into sheets

Garden, S.J.; Glidewell, C.; Low, J.N.; Skakle, J.M.S.; Wardell, J.L.

doi:10.1107/S0108270105000661

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 3| March 2005| Pages o145-o147

doi:10.1107/S0108270105000661

2-Iodo-6-methoxy-4-nitroaniline: tripartite ribbons built from N—H⋯O hydrogen bonds and iodo–nitro interactions are π-stacked into sheets

Simon J. Garden,^a Christopher Glidewell,^b ^* John N. Low,^c Janet M. S. Skakle ^c and James L. Wardell ^d

^aInstituto de Química, Departamento de Química Orgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, ^bSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 6 January 2005; accepted 7 January 2005; online 12 February 2005)

Molecules of the title compound, C₇H₇IN₂O₃, are linked by pairs of N—H⋯O hydrogen bonds into C(8)C(8)[ $[R_{2}^{2}]$ (6)] chains of rings, and antiparallel pairs of such chains are linked by a two-centre iodo–nitro interaction into tripartite ribbons. A single aromatic π–π stacking interaction links the ribbons into sheets.

Keywords: .

Comment

We report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1), which we compare with the simpler analogue 2-iodo-4-nitroaniline, (II) (McWilliam et al., 2001 ).

While the bond distances in (I) are generally similar to those found in both the triclinic and orthorhombic polymorphs of (II), denoted herein as (IIa) and (IIb), respectively, the molecular aggregation in (I) and (IIa) shows both similarities and differences. In compound (I), the molecules are linked into chains by pairs of N—H⋯O hydrogen bonds (Table 1). Amino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atoms H11 and H12, respectively, to the nitro atoms O1 and O2 in the molecule at (x − 1, y, z − 1), so generating by translation a C(8)C(8)[ $[R_{2}^{2}]$ (6)] chain of rings (Bernstein et al., 1995 ) running parallel to the [101] direction (Fig. 2). Within the $[R_{2}^{2}]$ (6) rings, the O⋯H angles are both 111° and the sum of the internal angles is 716°, so that this ring is effectively planar. The chain of rings can thus be regarded as a continuous sequence of planar hexagonal rings, in which the covalently bonded aryl rings alternate with hydrogen-bonded rings of almost the same size. In this connection, Desiraju (1995 ) has already drawn attention to the importance of ring size and shape, as opposed to ring composition, as an important factor in crystal engineering and molecular recognition.

Two such chains, related to one another by inversion and hence antiparallel, pass through each unit cell, and antiparallel pairs of chains are linked into a tripartite ribbon by a single two-centre iodo–nitro interaction [I2⋯O1ⁱ = 3.385 (3) Å, C2—I2⋯·O1ⁱ = 154.2 (2)°; symmetry code: (i) 1 − x, 2 − y, 2 − z]. In the central strip of this ribbon, centrosymmetric $[R_{2}^{2}]$ (12) rings (Starbuck et al., 1999 ), built up only from I⋯O interactions, alternate with centrosymmetric R₂⁴(12) rings, built up from both I⋯O interactions and N—H⋯O hydrogen bonds (Fig. 2). In addition, while the iodo substituents are all located in the interior of the ribbon, the methoxy substituents all lie on the outer edges of the ribbon.

These ribbons along [101] are linked into sheets by a single aromatic π–π stacking interaction. The aryl rings in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z) are strictly parallel, with an interplanar spacing of 3.321 (2) Å; the ring-centroid separation is 3.497 (2) Å, with a corresponding offset of 1.095 (2) Å. Propagation of this interaction by inversion then links each [101] ribbon to the two adjacent ribbons along the [011] direction, so linking the ribbons into ( $[\bar{1}]$ 11) sheets (Fig. 3).

The formation of the ribbon in (I) (Fig. 2) may be contrasted with the formation of sheets in (IIa). The very same hydrogen-bonded motif occurs in (IIa), generating a chain of rings, again by translation, although along the [01 $[\bar{1}]$ ] direction. However, the iodo–nitro interaction in (IIa), the dimensions of which are very similar to that in (I), links parallel hydrogen-bonded chains related by translation, so forming an (011) sheet containing just a single type of R₄⁴(20) ring between the hydrogen-bonded chains. The (011) sheets in (IIa) are linked into pairs by a centrosymmetric π–π stacking interaction. The different modes of the I⋯O linking of the hydrogen-bonded chains, by inversion in (I) and by translation in (IIa), is most plausibly ascribed to the presence of the methoxy substituent in (I). The continuous linking of hydrogen-bonded chains by translation is prevented in (I) simply by the steric bulk of the methoxy substituent, whereas linking in pairs by inversion is readily accomplished when the methoxy substituents are located on the outer edges of the ribbon.

By contrast, in the orthorhombic polymorph of (II), denoted here as (IIb), a single N—H⋯O hydrogen bond and a two-centre iodo–nitro interaction suffice to generate sheets of alternating R₄²(12) and R₄⁴(28) rings, which are themselves linked into a three-dimensional framework structure by means of a single π–π stacking interaction (McWilliam et al., 2001).

While the polymorphs (IIa) and (IIb) crystallize concomitantly from ethanol solution (McWilliam et al., 2001), we note a recent report that the thermodynamically less stable orthorhombic polymorph (IIb) can be selectively crystallized from ethanol in the presence of self-assembled monolayers of substituted mercaptobiphenyls, acting as specific templating agents (Hiremath et al., 2004 ).

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.

Figure 2
Part of the crystal structure of (I), showing the formation of a ribbon along [101]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), hash (#), dollar sign ($), ampersand (&) or `at' sign (@) are at the symmetry positions (x − 1, y, z − 1), (1 + x, y, 1 + z), (1 − x, 2 − y, 2 − z), (−x, 2 − y, 1 − z) and (2 − x, 2 − y, 3 − z), respectively.

Figure 3
A stereoview of part of the crystal structure of (I), showing the π-stacking of the [101] ribbons to form a ( $[\bar{1}]$ 11) sheet. For the sake of clarity, H atoms bonded to C atoms have been omitted.

Experimental

2-Methoxy-4-nitroaniline (1.68 g, 10 mmol) was dissolved in boiling methanol (25 ml). An aqueous solution of K[ICl₂] (10 ml, 2 M) (Garden et al., 2001 ) was slowly added to the boiling solution, after which the solution was maintained under reflux for a further 20 min. The reaction mixture was cooled and diluted with water (50 ml). The resulting solid was collected by filtration, washed with water and air-dried (2.88 g, 99% yield, m.p. 427–431 K). Recrystallization from aqueous ethanol gave thin yellow plates (m.p. 430–431 K). Crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in CHCl₃. ¹H NMR (CDCl₃): δ 3.96 (3H, s, OMe), 5.02 (2H, broad s, NH₂), 7.62 (1H, d, J = 2.4 Hz) and 8.23 (1H, d, J = 2.4 Hz) (aromatic); ¹³C NMR (CDCl₃): δ 56.6, 78.4, 105.5, 128.2, 139.1, 144.1 and 144.5.

Crystal data

C₇H₇IN₂O₃
M_r = 294.05
Triclinic, P $[\bar{1}]$
a = 8.0671 (3) Å
b = 8.0739 (4) Å
c = 8.6212 (5) Å
α = 112.616 (2)°
β = 115.060 (3)°
γ = 93.810 (3)°
V = 451.55 (4) Å³
Z = 2
D_x = 2.163 Mg m⁻³
Mo Kα radiation
Cell parameters from 2061 reflections
θ = 3.7–27.5°
μ = 3.52 mm⁻¹
T = 120 (2) K
Plate, yellow
0.10 × 0.06 × 0.03 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.720, T_max = 0.902
8665 measured reflections
2061 independent reflections
1845 reflections with I > 2σ(I)
R_int = 0.039
θ_max = 27.5°
h = −9 → 10
k = −10 → 10
l = −11 → 11

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.053
S = 1.00
2061 reflections
119 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0279P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.27 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O1ⁱ	0.88	2.36	3.007 (3)	130
N1—H12⋯O2ⁱ	0.88	2.45	3.028 (3)	124
Symmetry code: (i) x-1, y, z-1.

Crystals of (I) are triclinic; space group P $[\bar{1}]$ was selected and confirmed by the structure analysis. All H atoms were located from difference maps and then treated as riding atoms, with C—H = 0.95 (aromatic) or 0.98 Å (methyl) and N—H = 0.88 Å, and U_iso(H) = 1.2U_eq(C,N), or 1.5U_eq(C) for the methyl group.

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270105000661/sk1806sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105000661/sk1806Isup2.hkl

Comment top

We report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1), which we compare with the simpler analogue 2-iodo-4-nitroaniline, (II) (McWilliam et al., 2001).

While the bond distances in (I) are generally similar to those found in both the triclinic and orthorhombic polymorphs of (II), denoted herein as (IIa) and (IIb), respectively, the molecular aggregation in (I) and (IIa) shows both similarities and differences. In compound (I), the molecules are linked into chains by pairs of N—H···O hydrogen bonds (Table 1). The amino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atoms H11 and H12, respectively, to the nitro atoms O1 and O2 in the molecule at (x − 1, y, z − 1), so generating by translation a C(8) C(8)[R₂²(6)] chain of rings (Bernstein et al., 1995) running parallel to the [101] direction (Fig. 2). Within the R₂²(6) rings, the O···H angles are both 111° and the sum of the internal angles is 716°, so that this ring is effectively planar. The chain of rings can thus be regarded as a continuous sequence of planar hexagonal rings, in which the covalently bonded aryl rings alternate with hydrogen-bonded rings of almost the same size. In this connection, Desiraju (1995) has already drawn attention to the importance of ring size and shape, as opposed to ring composition, as an important factor in crystal engineering and molecular recognition.

Two such chains, related to one another by inversion and hence antiparallel, pass through each unit cell, and antiparallel pairs of chains are linked into a tripartite ribbon by a single two-centre iodo···nitro interaction [I2···O1ⁱ 3.385 (3) Å, C2—I2····O1ⁱ 154.2 (2)°; symmetry code: (i) 1 − x, 2 − y, 2 − z]. In the central strip of this ribbon, centrosymmetric R₂²(12) rings (Starbuck et al., 1999), built up only from I···O interactions, alternate with centrosymmetric R₂⁴(12) rings, built up from both I···O interactions and N—H···O hydrogen bonds (Fig. 2). In addition, while the iodo substituents are all located in the interior of the ribbon, the methoxy substituents all lie on the outer edges of the ribbon.

The formation of the ribbon in (I) (Fig. 2) may be contrasted with the formation of sheets in (IIa). The very same hydrogen-bonded motif occurs in (IIa), generating a chain of rings, again by translation, although along the [011] direction. However, the iodo–nitro interaction in (IIa), the dimensions of which are very similar to that in (I), links parallel hydrogen-bonded chains related by translation, so forming an (011) sheet containing just a single type of R₄⁴(20) ring between the hydrogen-bonded chains. The (011) sheets in (IIa) are linked into pairs by a centrosymmetric π–π stacking interaction. The different modes of the I···O linking of the hydrogen-bonded chains, by inversion in (I) and by translation in (IIa), is most plausibly ascribed to the presence of the methoxy substituent in (I). The continuous linking of hydrogen-bonded chains by translation is prevented in (I) simply by the steric bulk of the methoxy substituent, whereas linking in pairs by inversion is readily accomplished when the methoxy substituents are located on the outer edges of the ribbon.

By contrast, in the orthorhombic polymorph of (II), denoted here as (IIb), a single N—H···O hydrogen bond and a two-centre iodo···nitro interaction suffice to generate sheets of alternating R₄²(12) and R₄⁴(28) rings, which are themselves linked into a three-dimensional framework structure by means of a single π–π stacking interaction (McWilliam et al., 2001).

Experimental top

2-Methoxy-4-nitroaniline (1.68 g, 10 mmol) was dissolved in boiling methanol (25 ml). An aqueous solution of K[ICl₂] (10 ml, 2 M) (Garden et al., 2001) was slowly added to the boiling solution, after which the solution was maintained under reflux for a further 20 min. The reaction mixture was cooled and diluted with water (50 ml). The resulting solid was collected by filtration, washed with water and air-dried (2.88 g, 99% yield, m.p. 427–431 K). Recrystallization from aqueous ethanol gave thin yellow plates, m.p. 430–431 K. Crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in CHCl₃. Spectroscopic analysis: ¹H NMR (Solvent?, δ, p.p.m.): 3.96 (3H, s, OMe), 5.02 (2H, broad s, NH₂), 7.62 (1H, d, J = 2.4 Hz) and 8.23 (1H, d, J = 2.4 Hz) (aromatic); ¹³C NMR (Solvent?, δ, p.p.m.): 56.6, 78.4, 105.5, 128.2, 139.1, 144.1 and 144.5.

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 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.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a ribbon along [101]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*), hash (#), dollar sign ($), ampersand (&) or `at' sign (@) are at the symmetry positions (x − 1, y, z − 1), (1 + x, y, 1 + z), (1 − x, 2 − y, 2 − z), (−x, 2 − y, 1 − z) and (2 − x, 2 − y, 3 − z), respectively.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the π-stacking of the [101] ribbons to form a (111) sheet. For the sake of clarity, H atoms bonded to C atoms have been omitted.

2-Iodo-6-methoxy-4-nitroaniline top

Crystal data top

C₇H₇IN₂O₃	Z = 2
M_r = 294.05	F(000) = 280
Triclinic, P1	D_x = 2.163 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0671 (3) Å	Cell parameters from 2061 reflections
b = 8.0739 (4) Å	θ = 3.7–27.5°
c = 8.6212 (5) Å	µ = 3.52 mm⁻¹
α = 112.616 (2)°	T = 120 K
β = 115.060 (3)°	Plate, yellow
γ = 93.810 (3)°	0.10 × 0.06 × 0.03 mm
V = 451.55 (4) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	2061 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	1845 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.7°
ϕ and ω scans	h = −9→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
T_min = 0.720, T_max = 0.902	l = −11→11
8665 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0279P)²] where P = (F_o² + 2F_c²)/3
2061 reflections	(Δ/σ)_max = 0.001
119 parameters	Δρ_max = 1.27 e Å⁻³
0 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

C₇H₇IN₂O₃	γ = 93.810 (3)°
M_r = 294.05	V = 451.55 (4) Å³
Triclinic, P1	Z = 2
a = 8.0671 (3) Å	Mo Kα radiation
b = 8.0739 (4) Å	µ = 3.52 mm⁻¹
c = 8.6212 (5) Å	T = 120 K
α = 112.616 (2)°	0.10 × 0.06 × 0.03 mm
β = 115.060 (3)°

Data collection top

Nonius KappaCCD area-detector diffractometer	2061 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1845 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.902	R_int = 0.039
8665 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.053	H-atom parameters constrained
S = 1.00	Δρ_max = 1.27 e Å⁻³
2061 reflections	Δρ_min = −0.77 e Å⁻³
119 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I2	0.21628 (2)	0.90838 (2)	0.66781 (3)	0.02135 (8)
O1	0.7476 (3)	0.6384 (3)	1.0752 (3)	0.0265 (5)
O2	0.7049 (3)	0.3445 (3)	0.9016 (3)	0.0256 (5)
O6	0.1721 (3)	0.1987 (3)	0.2458 (3)	0.0194 (4)
N1	0.0624 (3)	0.5013 (4)	0.2886 (3)	0.0235 (6)
N4	0.6613 (3)	0.4922 (3)	0.9212 (3)	0.0190 (5)
C1	0.2056 (4)	0.5048 (4)	0.4476 (4)	0.0151 (6)
C2	0.2989 (4)	0.6607 (4)	0.6293 (4)	0.0149 (6)
C3	0.4480 (4)	0.6571 (4)	0.7856 (4)	0.0169 (6)
C4	0.5038 (4)	0.4954 (4)	0.7597 (4)	0.0151 (6)
C5	0.4153 (4)	0.3347 (4)	0.5824 (4)	0.0156 (6)
C6	0.2686 (4)	0.3417 (4)	0.4282 (4)	0.0162 (6)
C61	0.2159 (4)	0.0240 (4)	0.2147 (4)	0.0224 (6)
H3	0.5103	0.7640	0.9079	0.020*
H5	0.4550	0.2241	0.5686	0.019*
H11	0.0225	0.6014	0.2957	0.028*
H12	0.0094	0.3989	0.1783	0.028*
H61A	0.3503	0.0405	0.2487	0.034*
H61B	0.1361	−0.0667	0.0789	0.034*
H61C	0.1914	−0.0217	0.2952	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I2	0.02230 (12)	0.01713 (12)	0.02269 (12)	0.01023 (8)	0.00859 (8)	0.00921 (9)
O1	0.0306 (11)	0.0176 (11)	0.0140 (11)	0.0105 (9)	0.0000 (9)	0.0026 (9)
O2	0.0318 (11)	0.0166 (11)	0.0202 (11)	0.0142 (9)	0.0055 (9)	0.0077 (9)
O6	0.0186 (9)	0.0146 (10)	0.0142 (10)	0.0055 (8)	0.0014 (8)	0.0037 (8)
N1	0.0224 (12)	0.0182 (13)	0.0171 (13)	0.0084 (10)	0.0008 (10)	0.0055 (11)
N4	0.0206 (12)	0.0185 (13)	0.0141 (12)	0.0070 (10)	0.0052 (10)	0.0073 (11)
C1	0.0137 (13)	0.0180 (14)	0.0155 (14)	0.0042 (11)	0.0066 (11)	0.0099 (12)
C2	0.0170 (13)	0.0107 (13)	0.0174 (14)	0.0061 (11)	0.0081 (11)	0.0068 (11)
C3	0.0184 (13)	0.0149 (14)	0.0149 (14)	0.0035 (11)	0.0067 (11)	0.0062 (12)
C4	0.0132 (12)	0.0187 (15)	0.0088 (13)	0.0039 (11)	0.0018 (10)	0.0059 (11)
C5	0.0169 (13)	0.0154 (14)	0.0155 (14)	0.0053 (11)	0.0071 (11)	0.0087 (12)
C6	0.0156 (13)	0.0134 (14)	0.0127 (14)	0.0020 (11)	0.0043 (11)	0.0028 (11)
C61	0.0247 (15)	0.0134 (15)	0.0168 (15)	0.0040 (12)	0.0045 (12)	0.0021 (12)

Geometric parameters (Å, º) top

C1—N1	1.356 (3)	C4—N4	1.445 (3)
C1—C2	1.401 (4)	N4—O2	1.234 (3)
C1—C6	1.418 (4)	N4—O1	1.242 (3)
N1—H11	0.88	C5—C6	1.381 (4)
N1—H12	0.88	C5—H5	0.95
C2—C3	1.388 (4)	C6—O6	1.363 (3)
C2—I2	2.100 (3)	O6—C61	1.429 (4)
C3—C4	1.377 (4)	C61—H61A	0.98
C3—H3	0.95	C61—H61B	0.98
C4—C5	1.399 (4)	C61—H61C	0.98

N1—C1—C2	124.3 (3)	O2—N4—C4	119.0 (2)
N1—C1—C6	118.0 (3)	O1—N4—C4	118.6 (2)
C2—C1—C6	117.7 (2)	C6—C5—C4	118.0 (3)
C1—N1—H11	120.0	C6—C5—H5	121.0
C1—N1—H12	120.0	C4—C5—H5	121.0
H11—N1—H12	120.0	O6—C6—C5	124.9 (3)
C3—C2—C1	121.6 (3)	O6—C6—C1	113.5 (2)
C3—C2—I2	118.6 (2)	C5—C6—C1	121.6 (2)
C1—C2—I2	119.83 (19)	C6—O6—C61	117.7 (2)
C4—C3—C2	118.6 (3)	O6—C61—H61A	109.5
C4—C3—H3	120.7	O6—C61—H61B	109.5
C2—C3—H3	120.7	H61A—C61—H61B	109.5
C3—C4—C5	122.5 (2)	O6—C61—H61C	109.5
C3—C4—N4	118.8 (2)	H61A—C61—H61C	109.5
C5—C4—N4	118.7 (2)	H61B—C61—H61C	109.5
O2—N4—O1	122.4 (2)

N1—C1—C2—C3	−178.3 (3)	C5—C4—N4—O1	175.5 (3)
C6—C1—C2—C3	0.1 (4)	C3—C4—C5—C6	1.1 (4)
N1—C1—C2—I2	0.6 (4)	N4—C4—C5—C6	−178.2 (3)
C6—C1—C2—I2	179.0 (2)	C4—C5—C6—O6	178.2 (3)
C1—C2—C3—C4	−0.2 (4)	C4—C5—C6—C1	−1.2 (4)
I2—C2—C3—C4	−179.2 (2)	N1—C1—C6—O6	−0.3 (4)
C2—C3—C4—C5	−0.4 (4)	C2—C1—C6—O6	−178.8 (2)
C2—C3—C4—N4	178.9 (2)	N1—C1—C6—C5	179.1 (3)
C3—C4—N4—O2	175.9 (3)	C2—C1—C6—C5	0.6 (4)
C5—C4—N4—O2	−4.8 (4)	C5—C6—O6—C61	5.0 (4)
C3—C4—N4—O1	−3.8 (4)	C1—C6—O6—C61	−175.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O1ⁱ	0.88	2.36	3.007 (3)	130
N1—H12···O2ⁱ	0.88	2.45	3.028 (3)	124

Symmetry code: (i) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₇H₇IN₂O₃
M_r	294.05
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.0671 (3), 8.0739 (4), 8.6212 (5)
α, β, γ (°)	112.616 (2), 115.060 (3), 93.810 (3)
V (Å³)	451.55 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.52
Crystal size (mm)	0.10 × 0.06 × 0.03

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.720, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	8665, 2061, 1845
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.053, 1.00
No. of reflections	2061
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.27, −0.77

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O1ⁱ	0.88	2.36	3.007 (3)	130
N1—H12···O2ⁱ	0.88	2.45	3.028 (3)	124

Symmetry code: (i) x−1, y, z−1.

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311–2327. CrossRef CAS Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Garden, S. J., Torres, J. C., Souza Melo, S. C., Lima, A. S., Pinto, A. C. & Lima, E. L. S. (2001). Tetrahedron Lett. 42, 2089–2092. Web of Science CrossRef CAS Google Scholar
Hiremath, R., Varney, S. W. & Swift, J. A. (2004). Chem. Commun. pp. 2676–2677. CrossRef Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
McWilliam, S. A., Skakle, J. M. S., Low, J. N., Wardell, J. L., Garden, S. J., Pinto, A. C., Torres, J. C. & Glidewell, C. (2001). Acta Cryst. C57, 942–945. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
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ISSN: 2053-2296

Volume 61| Part 3| March 2005| Pages o145-o147

doi:10.1107/S0108270105000661

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Iodo-6-meth­oxy-4-nitro­aniline: tripartite ribbons built from N—H⋯O hydrogen bonds and iodo–nitro interactions are π-stacked into sheets

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-Iodo-6-methoxy-4-nitroaniline: tripartite ribbons built from N—H⋯O hydrogen bonds and iodo–nitro interactions are π-stacked into sheets