Hydro­gen bonding in substituted nitro­anilines: hydrogen-bonded sheets in 4-iodo-3-nitro­aniline

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

doi:10.1107/S0108270104006092

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 5| May 2004| Pages o328-o330

doi:10.1107/S0108270104006092

Hydrogen bonding in substituted nitroanilines: hydrogen-bonded sheets in 4-iodo-3-nitroaniline

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

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

(Received 3 March 2004; accepted 15 March 2004; online 9 April 2004)

In the title compound, C₆H₅IN₂O₂, the nitro group is disordered over two sets of sites, each with 0.5 occupancy, and the amino N atom is pyramidal. The molecules are linked into sheets by a combination of three-centre N—H⋯(O)₂ hydrogen bonds involving alternative pairs of O-atom sites and two-centre N—H⋯N hydrogen bonds involving the pyramidal amino group.

Comment

We have recently reported the molecular and supramolecular structures of a number of iodonitroanilines, no two of which exhibit in their supramolecular structures the same pattern of N—H⋯O hydrogen bonds, iodo–nitro interactions or aromatic π–π stacking interactions (Garden, Glidewell et al., 2001 ; McWilliam et al., 2001 , Garden et al., 2002 ).

Iodination of 3-nitroaniline using a solution of K[ICl₂] in methanol as the iodinating agent (Larsen et al., 1956 ; Garden, Torres et al., 2001 ) gave, in addition to 2-iodo-5-nitroaniline, (I), and 2,4-diiodo-3-nitroaniline, (II), a third compound in very low yield. This is presumably an intermediate in the formation of (II), viz. either 2-iodo-3-nitroaniline, (III), or more plausibly 4-iodo-3-nitroaniline, (IV), but it had not been isolated when the structures of (I) and (II) were reported (Garden et al., 2002). This intermediate has now been isolated and crystallized and we report here the molecular and supramolecular structures of this product, 4-iodo-3-nitroaniline, (IV). The supramolecular structure proves to be different from any of those adopted by its isomers (I), (V) and (VI).

The O atoms of the nitro group in (IV) are disordered over two sets of sites of equal occupancy (Fig. 1). The nitro groups defined by atoms O3A and O3B on the one hand and O3C and O3D on the other are both twisted out of the plane of the aryl ring by ca 13° and ca 35°, respectively, such that the dihedral angle between the two nitro-group planes is ca 48°. However, despite their equal occupancies, the occupation of the two alternative sets of sites cannot be entirely random. In order to avoid a very short contact of 2.518 (12) Å between atoms O3C and O3D in the molecules at (x, y, z) and (x, 1 + y, z), respectively, adjacent molecular sites related by translation along [010] cannot both accommodate the nitro-group orientation involving atoms O3C and O3D. Since both orientations must occur with equal frequency in a given [010] stack, there must be a strict alternation along [010] of the occupation of the two alternative sets of sites. Hence, there must be perfect correlation of the occupancies along any one [010] stack, although without any necessary correlation of the occupancies in any given [010] stack with those in the neighbouring stacks. Accordingly, the structure is correctly described in terms of the present unit cell with Z = 4, rather than of a larger unit cell with Z = 8.

The amino N atom is pyramidal, as judged by the locations of the corresponding H atoms found from difference maps. Consistent with this, the C1—N1 distance of 1.388 (5) Å is typical of C_aryl—NH₂ distances involving pyramidal nitrogen (mean value 1.394 Å and lower quartile value 1.385 Å; Allen et al., 1987 ), rather than of those involving planar N (mean value 1.355 Å and upper quartile value 1.372 Å). The remaining bond distances show no unusual values.

The supramolecular structure of compound (IV) is determined by a combination of an asymmetric three-centre N—H⋯(O)₂ hydrogen bond and a two-centre N—H⋯N hydrogen bond (Table 1). However, X—H⋯π(arene) hydrogen bonds (X is C or N), intermolecular iodo–nitro interactions and aromatic π–π stacking interactions are all absent.

The amino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H1A, to O atoms in the molecule at ( $[{1 \over 2}]$ + x, $[{3 \over 2}]$ − y, $[{1 \over 2}]$ + z), either to both O3A and O3B in one orientation of the nitro group, or to both O3C and O3D in the other orientation. No matter which pair of O-atom sites is occupied, the molecules at (x, y, z) and ( $[{1 \over 2}]$ + x, $[{3 \over 2}]$ − y, $[{1 \over 2}]$ + z) are linked by a nearly planar three-centre interaction. Propagation of this interaction then produces a C(7)[R₁²(4)] (Bernstein et al., 1995 ) chain of rings running parallel to the [101] direction and generated by the n-glide plane at y = $[{3 \over 4}]$ (Fig. 2).

The [101] chains are linked by the nearly linear two-centre N—H⋯N hydrogen bond, in which amino atom N1 in the molecule at (x, y, z) acts as donor, via atom H1B, to atom N1 in the molecule at ( $[{1 \over 2}]$ − x, $[{1 \over 2}]$ + y, $[{3 \over 2}]$ − z), thereby forming a C(2) chain running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[{1 \over 4}]$ , y, $[{3 \over 4}]$ ) (Fig. 3). The combination of the [101] and [010] chains generates a (10 $[\overline 1]$ ) sheet (Fig. 4) in the form of a (4,4)-net (Batten & Robson, 1998 ).

It is of interest to compare very briefly the rather simple supramolecular structure of compound (IV) with those of the isomers (I), (V) and (VI). In (I), hydrogen-bonded dimers are linked into sheets by two-centre iodo–nitro interactions, and these sheets are linked into a three-dimensional framework by aromatic π–π stacking interactions (Garden et al., 2002). In compound (V), where Z′ = 2, each of the two independent molecules forms sheets via a combination of N—H⋯O hydrogen bonds and two-centre iodo–nitro interactions, but there are no direction-specific interactions between the two types of sheet (Garden et al., 2002). Compound (VI) forms two polymorphs and in each a combination of hydrogen bonds and iodo–nitro interactions generates sheets, which are linked by aromatic π–π stacking interactions into bilayers in the triclinic polymorph and into a three-dimensional framework in the orthorhombic polymorph (McWilliam et al., 2001). It is striking that iodo–nitro interactions are present in the structures of each of compounds (I), (V) and (VI), but that these interactions are absent from the structure of (IV).

Figure 1
The molecule of (IV

), showing the atom-labelling scheme and the disordered O atoms. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of (IV

), showing the formation of the hydrogen-bonded chain of rings along [101]. For the sake of clarity, H atoms bonded to C atoms have been omitted, and only one pair of O atoms, O3A and O3B, is shown. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions ( $[{1 \over 2}]$ + x, $[{3 \over 2}]$ − y, $[{1 \over 2}]$ + z), (1 + x, y, 1 + z) and (x − $[{1 \over 2}]$ , $[{3 \over 2}]$ − y, z − $[{1 \over 2}]$ ), respectively.

Figure 3
Part of the crystal structure of (IV

), showing the formation of the hydrogen-bonded chain along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted, and only one orientation of the disordered nitro group is shown. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions ( $[{1 \over 2}]$ − x, $[{1 \over 2}]$ + y, $[{3 \over 2}]$ − z), (x, 1 + y, z) and ( $[{1 \over 2}]$ − x, y − $[{1 \over 2}]$ , $[{3 \over 2}]$ − z), respectively.

Figure 4
A stereoview of part of the crystal structure of (IV

), showing the formation of the (10 $[\overline 1]$ ) sheet resulting from the combination of [101] and [010] chains. For the sake of clarity, H atoms bonded to C atoms have been omitted, and only one orientation of the disordered nitro group is shown.

Experimental

For the preparation of (IV), a solution of K[ICl₂] (2.5 ml, 2 M) in water was added to a solution of 3-nitroaniline (10 mmol) in MeOH (18 ml). The reaction mixture was left at room temperature for a few hours, then heated to boiling and diluted with water (10 ml). The precipitate which formed on cooling was collected, washed with cold 50% aqueous methanol, and recrystallized from 50% aqueous methanol to give a cocrystallized mixture of 2-iodo-5-nitroaniline, (I), and 4-iodo-3-nitroaniline, (IV). These compounds were separated by column chromatography on silica gel using hexane–CH₂Cl₂ (1:1 v/v) as eluant. 4-Iodo-3-nitroaniline (0.60 g, 45% yield based on K[ICl₂]; m.p. 414–415 K) was recrystallized from aqueous methanol. ¹H NMR (CDCl₃/DMSO-d₆, δ): 4.90 (2H, br, s, NH₂), 6.62 (1H, H6, dd, J = 2.7 and 8.6 Hz), 7.20 (1H, H2, d, J = 2.7 Hz), 7.62 (1H, H5, d, J = 8.7 Hz); ¹³C NMR (CDCl₃/DMSO-d₆, δ): 67.6 (C—I), 110.7 (CH), 119.6 (CH), 141.1 (CH), 148.5 (C—NH₂), 153.1 (C—NO₂).

Crystal data

C₆H₅IN₂O₂
M_r = 264.02
Monoclinic, P2₁/n
a = 12.5174 (7) Å
b = 4.2601 (3) Å
c = 16.0042 (9) Å
β = 111.580 (1)°
V = 793.61 (8) Å³
Z = 4
D_x = 2.210 Mg m⁻³
Mo Kα radiation
Cell parameters from 2848 reflections
θ = 2.6–32.5°
μ = 3.99 mm⁻¹
T = 291 (2) K
Plate, colourless
0.50 × 0.05 × 0.05 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
φ/ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.456, T_max = 0.819
8259 measured reflections
2848 independent reflections
1971 reflections with I > 2σ(I)
R_int = 0.028
θ_max = 32.5°
h = −17 → 18
k = −4 → 6
l = −22 → 24

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.00
2848 reflections
100 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0553P)² + 0.2861P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 1.10 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3Aⁱ	0.88	2.50	3.265 (8)	146
N1—H1A⋯O3Bⁱ	0.88	2.35	3.148 (8)	150
N1—H1A⋯O3Dⁱ	0.88	2.58	3.298 (8)	140
N1—H1A⋯O3Cⁱ	0.88	2.46	3.295 (8)	158
N1—H1B⋯N1ⁱⁱ	0.88	2.25	3.105 (6)	164
Symmetry codes: (i) $[{\script{1\over 2}}+x,{\script{3\over 2}}-y,{\script{1\over 2}}+z]$ ; (ii) $[{\script{1\over 2}}-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ .

The space group P2₁/n was uniquely assigned from the systematic absences. All H atoms were located from difference maps. H atoms bonded to C atoms were treated as riding atoms along the bisectors of the external angles of the aryl ring, with C—H distances of 0.93 Å. The sites of the H atoms bonded to atom N1 showed clearly the pyramidal geometry of the amino group; these H atoms were allowed to ride at the sites found from the difference maps, with the N—H distances constrained to 0.88 Å. For all H atoms, U_iso(H) = 1.2U_eq(C,N). It was found necessary to assign equal anisotropic displacement parameters to the partial O-atom sites in order to achieve satisfactory refinements of the O atoms. When the site-occupancy factors of the O atoms in the alternative orientations of the nitro group were then refined, they gave values of 0.51 (3) and 0.49 (3); these occupancies were all thereafter fixed at 0.50.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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/S0108270104006092/gg1211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104006092/gg1211Isup2.hkl

Comment top

We have recently reported the molecular and supramolecular structures of a number of iodo-nitroanilines, no two of which exhibit in their supramolecular structures the same pattern of N—H···O hydrogen bonds, iodo···nitro interactions or aromatic π–π stacking interactions (Garden, Glidewell et al., 2001; McWilliam et al., 2001, Garden et al., 2002).

Iodination of 3-nitroaniline, using a solution of K[ICl₂] in methanol as the iodinating agent (Larsen et al., 1956; Garden, Torres et al., 2001) gave, in addition to 2-iodo-5-nitroaniline, (I), and 2,4-diiodo-3-nitroaniline, (II), a third compound, in very low yield. This is presumably an intermediate in the formation of (II), either 2-iodo-3-nitroaniline, (III), or, more plausibly, 4-iodo-3-nitroaniline, (IV), but it had not been isolated when the structures of (I) and (II) were reported (Garden et al., 2002). This compound has now been isolated and crystallized, and we report here the molecular and supramolecular structures of this product, 4-iodo-3-nitroaniline, (IV). The supramolecular structure proves to be different from any of those adopted by its isomers (I), (V) and (VI). \sch

The O atoms of the nitro group in (IV) are disordered over two sets of sites of equal occupancy (Fig. 1). The nitro groups defined by atoms O3A and O3B, on the one hand, and O3C and O3D on the other, are both twisted out of the plane of the aryl ring by ca 13 and ca 35°, respectively, such that the dihedral angle between the two nitro-group planes is ca 48°. However, despite their equal occupancies, the occupation of the two alternative sets of sites cannot be entirely random. In order to avoid a very short contact of 2.518 (12) Å between atoms O3C and O3D in the molecules at (x, y, z) and (x, 1 + y, z), respectively, adjacent molecular sites related by translation along [010] cannot both accommodate the nitro-group orientation involving atoms O3C and O3D. Since both orientations must occur with equal frequency in a given [010] stack, there must be a strict alternation along [010] of the occupation of the two alternative sets of sites. Hence, there must be perfect correlation of the occupancies along any one [010] stack, although without any necessary correlation of the occupancies in any given [010] stack with those in the neighbouring stacks. Accordingly, the structure is correctly described in terms of the present unit cell with Z = 4, rather than of a larger unit cell with Z = 8.

The amino N atom is pyramidal, as judged by the locations of the corresponding H atoms found from difference maps. Consistent with this, the C1—N1 distance of 1.388 (5) Å is typical of C(aryl)-NH₂ distances involving pyramidal N (mean value 1.394 Å, lower quartile value 1.385 Å; Allen et al., 1987), rather than of those involving planar N (mean value 1.355 Å, upper quartile value 1.372 Å). The remaining bond distances show no unusual values.

The supramolecular structure of compound (IV) is determined by a combination of an asymmetric three-centre N—H···(O)₂ hydrogen bond and a two-centre N—H···N hydrogen bond (Table 1). However, X—H···π(arene) hydrogen bonds (X is C or N), intermolecular iodo···nitro interactions and aromatic π–π stacking interactions are all absent.

The amino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H1A, to O atoms in the molecule at (1/2 + x, 3/2 − y, 1/2 + z), either to both O3A and O3B in one orientation of the nitro group, or to both O3C and O3D in the other orientation. No matter which pair of O sites is occupied, the molecules at (x, y, z) and (1/2 + x, 3/2 − y, 1/2 + z) are linked by a nearly-planar three-centre interaction. Propagation of this interaction then produces a C(7)[R₁²(4)] (Bernstein et al., 1995) chain of rings running parallel to the [101] direction and generated by the n-glide plane at y = 3/4 (Fig. 2).

The [101] chains are linked by the nearly-linear two-centre N—H···N hydrogen bond, in which amino atom N1 in the molecule at (x, y, z) acts as donor, via atom H1B, to atom N1 in the molecule at (1/2 − x, 1/2 + y, 3/2 − z), thereby forming a C(2) chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1/4, y, 3/4) (Fig. 3). The combination of the [101] and [010] chains generates a (101) sheet (Fig. 4) in the form of a (4,4) net (Batten & Robson, 1998).

It is of interest to compare very briefly the rather simple supramolecular structure of compound (IV) with those of the isomers (I), (V) and (VI). In (I), hydrogen-bonded dimers are linked into sheets by a two-centre iodo···nitro interactions, and these sheets are linked into a three-dimensional framework by aromatic π–π stacking interactions (Garden et al., 2002). In compound (V), where Z' = 2, each of the two independent molecules forms sheets via a combination of N—H···O hydrogen bonds and two-centre iodo···nitro interactions, but there are no direction-specific interactions between the two types of sheet (Garden et al., 2002). Compound (VI) forms two polymorphs, and in each a combination of hydrogen bonds and iodo···nitro interactions generates sheets, which are linked by aromatic π–π stacking interactions into bilayers in the triclinic polymorph and into a three-dimensional framework in the orthorhombic polymorph (McWilliam et al., 2001). It is striking that iodo···nitro interactions are present in the structures of each of compounds (I), (V) and (VI), but that these interactions are absent from the structure of (IV).

Experimental top

For the preparation of (IV), a solution of K[ICl₂] (2.5 ml, 2 M) in water was added to a solution of 3-nitroaniline (10 mmol) in MeOH (18 ml). The reaction mixture was left at room temperature for a few hours, then heated to boiling and diluted with water (10 ml). The precipitate which formed on cooling was collected, washed with cold 50% aqueous methanol, and recrystallized from 50% aqueous methanol to give a co-crystallized mixture of 2-iodo-5-nitroaniline, (I), and 4-iodo-3-nitroaniline, (IV). These compounds were separated by column chromatography on silica gel using hexane/CH₂Cl₂ (Ratio?) as eluent. 4-Iodo-3-nitroaniline (0.60 g, 45% yield based upon K[ICl₂], m.p. 414–415 K) was recrystallized from aqueous methanol. ¹H NMR (CDCl₃/DMSO-d₆, δ, p.p.m.): 4.90 (2H, br, s, NH₂), 6.62 (1H, H-6, dd, J = 2.7 and8.6 Hz), 7.20 (1H, H-2, d, J = 2.7 Hz), 7.62 (1H, H-5, d, J = 8.7 Hz); ¹³C NMR (CDCl₃/DMSO-d₆, δ, p.p.m.): 67.6 (C—I), 110.7 (CH), 119.6 (CH), 141.1 (CH), 148.5 (C—NH₂), 153.1 (C—NO₂).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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 (IV), showing the atom-labelling scheme and the disordered O atoms. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (IV), showing formation of the hydrogen-bonded chain of rings along [101]. For the sake of clarity, H atoms bonded to C atoms have been omitted, and only one pair of O atoms, O3A and O3B, is shown. The atoms marked with an asterisk (*), hash (#) or dollar sign () are at the symmetry positions (1/2 + x, 3/2 − y, 1/2 + z), (1 + x, y, 1 + z) and (x − 1/2, 3/2 − y, z − 1/2), respectively.
	Fig. 3. Part of the crystal structure of (IV), showing formation of the hydrogen-bonded chain along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted, and only one orientation of the disordered nitro group is shown. The atoms marked with an asterisk (*), hash (#) or dollar sign () are at the symmetry positions (1/2 − x, 1/2 + y, 3/2 − z), (x, 1 + y, z) and (1/2 − x, y − 1/2, 3/2 − z), respectively.
	Fig. 4. A stereoview of part of the crystal structure of (IV), showing formation of the (101) sheet resulting from the combination of [101] and [010] chains. For the sake of clarity, H atoms bonded to C atoms have been omitted, and only one orientation of the disordered nitro group is shown.

4-iodo-3-nitroaniline top

Crystal data top

C₆H₅IN₂O₂	F(000) = 496
M_r = 264.02	D_x = 2.210 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2848 reflections
a = 12.5174 (7) Å	θ = 2.6–32.5°
b = 4.2601 (3) Å	µ = 3.99 mm⁻¹
c = 16.0042 (9) Å	T = 291 K
β = 111.580 (1)°	Plate, colourless
V = 793.61 (8) Å³	0.50 × 0.05 × 0.05 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2848 independent reflections
Radiation source: fine-focus sealed X-ray tube	1971 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ/ω scans	θ_max = 32.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→18
T_min = 0.456, T_max = 0.819	k = −4→6
8259 measured reflections	l = −22→24

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0553P)² + 0.2861P] where P = (F_o² + 2F_c²)/3
2848 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 1.10 e Å⁻³
0 restraints	Δρ_min = −0.85 e Å⁻³

Crystal data top

C₆H₅IN₂O₂	V = 793.61 (8) Å³
M_r = 264.02	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.5174 (7) Å	µ = 3.99 mm⁻¹
b = 4.2601 (3) Å	T = 291 K
c = 16.0042 (9) Å	0.50 × 0.05 × 0.05 mm
β = 111.580 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2848 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1971 reflections with I > 2σ(I)
T_min = 0.456, T_max = 0.819	R_int = 0.028
8259 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.00	Δρ_max = 1.10 e Å⁻³
2848 reflections	Δρ_min = −0.85 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
I4	0.28665 (2)	0.16650 (6)	0.356645 (15)	0.06100 (12)
O3A	0.0122 (6)	0.682 (2)	0.4378 (5)	0.0840 (15)	0.50
O3B	0.0796 (6)	0.538 (2)	0.3416 (5)	0.0840 (15)	0.50
O3C	0.0469 (6)	0.833 (2)	0.4266 (6)	0.0840 (15)	0.50
O3D	0.0510 (6)	0.376 (2)	0.3657 (5)	0.0840 (15)	0.50
N1	0.3297 (3)	0.7166 (11)	0.7327 (2)	0.0707 (10)
N3	0.0928 (3)	0.5822 (9)	0.4213 (2)	0.0567 (8)
C1	0.3197 (3)	0.6074 (10)	0.6485 (2)	0.0521 (8)
C2	0.2173 (3)	0.6486 (9)	0.5757 (2)	0.0460 (7)
C3	0.2052 (2)	0.5254 (9)	0.49309 (19)	0.0436 (6)
C4	0.2922 (3)	0.3615 (8)	0.4779 (2)	0.0455 (7)
C5	0.3944 (3)	0.3240 (10)	0.5519 (3)	0.0563 (9)
C6	0.4073 (3)	0.4401 (12)	0.6344 (2)	0.0598 (10)
H1A	0.3986	0.7221	0.7752	0.085*
H1B	0.2745	0.8462	0.7316	0.085*
H2	0.1570	0.7589	0.5828	0.055*
H5	0.4552	0.2172	0.5446	0.068*
H6	0.4761	0.4068	0.6824	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I4	0.0921 (2)	0.04963 (16)	0.04865 (15)	0.00516 (12)	0.03457 (13)	0.00129 (10)
O3A	0.056 (2)	0.112 (5)	0.065 (2)	0.007 (2)	−0.0015 (17)	−0.016 (3)
O3B	0.056 (2)	0.112 (5)	0.065 (2)	0.007 (2)	−0.0015 (17)	−0.016 (3)
O3C	0.056 (2)	0.112 (5)	0.065 (2)	0.007 (2)	−0.0015 (17)	−0.016 (3)
O3D	0.056 (2)	0.112 (5)	0.065 (2)	0.007 (2)	−0.0015 (17)	−0.016 (3)
N1	0.0607 (18)	0.103 (3)	0.0408 (15)	−0.0103 (19)	0.0096 (13)	−0.0162 (18)
N3	0.0464 (15)	0.073 (2)	0.0440 (15)	−0.0001 (15)	0.0084 (12)	−0.0019 (14)
C1	0.0466 (16)	0.066 (2)	0.0384 (14)	−0.0117 (15)	0.0097 (12)	−0.0046 (14)
C2	0.0407 (14)	0.0572 (19)	0.0378 (13)	−0.0006 (14)	0.0117 (11)	−0.0030 (14)
C3	0.0429 (14)	0.0466 (17)	0.0371 (13)	−0.0054 (13)	0.0095 (11)	0.0022 (13)
C4	0.0556 (17)	0.0443 (16)	0.0369 (13)	−0.0003 (14)	0.0175 (12)	0.0044 (13)
C5	0.0477 (16)	0.069 (2)	0.0506 (18)	0.0112 (17)	0.0157 (14)	0.0104 (18)
C6	0.0455 (16)	0.079 (3)	0.0461 (17)	−0.0011 (18)	0.0066 (13)	0.0106 (18)

Geometric parameters (Å, º) top

C1—N1	1.388 (5)	N3—O3A	1.211 (9)
C1—C2	1.390 (4)	N3—O3D	1.223 (8)
C1—C6	1.393 (6)	N3—O3C	1.232 (9)
N1—H1A	0.88	N3—O3B	1.239 (8)
N1—H1B	0.88	C4—C5	1.396 (5)
C2—C3	1.379 (5)	C4—I4	2.089 (3)
C2—H2	0.93	C5—C6	1.363 (6)
C3—C4	1.388 (5)	C5—H5	0.93
C3—N3	1.472 (4)	C6—H6	0.93

N1—C1—C2	119.8 (4)	O3C—N3—O3B	108.3 (7)
N1—C1—C6	122.2 (3)	O3A—N3—C3	121.4 (4)
C2—C1—C6	117.9 (3)	O3D—N3—C3	118.7 (5)
C1—N1—H1A	118.2	O3C—N3—C3	115.2 (4)
C1—N1—H1B	113.7	O3B—N3—C3	120.4 (4)
H1A—N1—H1B	122.5	C3—C4—C5	116.3 (3)
C3—C2—C1	119.8 (3)	C3—C4—I4	127.1 (2)
C3—C2—H2	120.1	C5—C4—I4	116.7 (3)
C1—C2—H2	120.1	C6—C5—C4	121.7 (4)
C2—C3—C4	122.9 (3)	C6—C5—H5	119.2
C2—C3—N3	115.0 (3)	C4—C5—H5	119.2
C4—C3—N3	122.1 (3)	C5—C6—C1	121.4 (3)
O3A—N3—O3D	104.1 (6)	C5—C6—H6	119.3
O3D—N3—O3C	126.0 (5)	C1—C6—H6	119.3
O3A—N3—O3B	118.2 (5)

N1—C1—C2—C3	−176.5 (4)	C4—C3—N3—O3B	−13.8 (8)
C6—C1—C2—C3	−0.1 (5)	C2—C3—C4—C5	0.5 (5)
C1—C2—C3—C4	−0.7 (5)	N3—C3—C4—C5	−179.9 (3)
C1—C2—C3—N3	179.7 (3)	C2—C3—C4—I4	−179.4 (3)
C2—C3—N3—O3A	−11.7 (8)	N3—C3—C4—I4	0.3 (5)
C4—C3—N3—O3A	168.6 (7)	C3—C4—C5—C6	0.5 (6)
C2—C3—N3—O3D	−143.1 (6)	I4—C4—C5—C6	−179.6 (3)
C4—C3—N3—O3D	37.3 (7)	C4—C5—C6—C1	−1.3 (7)
C2—C3—N3—O3C	33.2 (7)	N1—C1—C6—C5	177.4 (4)
C4—C3—N3—O3C	−146.5 (6)	C2—C1—C6—C5	1.1 (6)
C2—C3—N3—O3B	165.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3Aⁱ	0.88	2.50	3.265 (8)	146
N1—H1A···O3Bⁱ	0.88	2.35	3.148 (8)	150
N1—H1A···O3Dⁱ	0.88	2.58	3.298 (8)	140
N1—H1A···O3Cⁱ	0.88	2.46	3.295 (8)	158
N1—H1B···N1ⁱⁱ	0.88	2.25	3.105 (6)	164

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₆H₅IN₂O₂
M_r	264.02
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	12.5174 (7), 4.2601 (3), 16.0042 (9)
β (°)	111.580 (1)
V (Å³)	793.61 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.99
Crystal size (mm)	0.50 × 0.05 × 0.05

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.456, 0.819
No. of measured, independent and observed [I > 2σ(I)] reflections	8259, 2848, 1971
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.00
No. of reflections	2848
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.10, −0.85

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2000), SAINT, 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—H1A···O3Aⁱ	0.88	2.50	3.265 (8)	146
N1—H1A···O3Bⁱ	0.88	2.35	3.148 (8)	150
N1—H1A···O3Dⁱ	0.88	2.58	3.298 (8)	140
N1—H1A···O3Cⁱ	0.88	2.46	3.295 (8)	158
N1—H1B···N1ⁱⁱ	0.88	2.25	3.105 (6)	164

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, y+1/2, −z+3/2.

Acknowledgements

X-ray data were collected at the University of Aberdeen; the authors thank the University of Aberdeen for funding the purchase of the diffractometer. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. SLG and JLW thank CNPq and FAPERJ for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Bruker (2000). SADABS (Version 2.03) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Volume 60| Part 5| May 2004| Pages o328-o330

doi:10.1107/S0108270104006092

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

Hydro­gen bonding in substituted nitro­anilines: hydrogen-bonded sheets in 4-iodo-3-nitro­aniline

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Hydrogen bonding in substituted nitroanilines: hydrogen-bonded sheets in 4-iodo-3-nitroaniline