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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

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

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 ππ stacking interaction links the ribbons into sheets.

Keywords: .

Comment

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

[Scheme 1]

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[link]). 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[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) running parallel to the [101] direction (Fig. 2[link]). 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[Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311-2327.]) 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[Starbuck, J., Norman, N. C. & Orpen, A. G. (1999). New J. Chem. 23, 969-972.]), 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[link]). 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 ππ 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[link]).

The formation of the ribbon in (I) (Fig. 2[link]) 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 ππ 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 ππ stacking interaction (McWilliam et al., 2001[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.]).

While the polymorphs (IIa) and (IIb) crystallize concomitantly from ethanol solution (McWilliam et al., 2001[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.]), 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[Hiremath, R., Varney, S. W. & Swift, J. A. (2004). Chem. Commun. pp. 2676-2677.]).

[Figure 1]
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]
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]
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[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.]) 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

  • Mr = 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

  • Dx = 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[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.720, Tmax = 0.902

  • 8665 measured reflections

  • 2061 independent reflections

  • 1845 reflections with I > 2σ(I)

  • Rint = 0.039

  • θmax = 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(Fo2) + (0.0279P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 1.27 e Å−3

  • Δρmin = −0.77 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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 Uiso(H) = 1.2Ueq(C,N), or 1.5Ueq(C) for the methyl group.

Data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[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.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


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.

These ribbons along [101] are linked into sheets by a single aromatic ππ 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 (111) 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 [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 ππ 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 ππ 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).

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.

Refinement top

Crystals of compound (I) are triclinic; space group P1 was selected, and confirmed by the structure analysis. All H atoms were located from difference maps and then treated as riding atoms, with distances C—H = 0.95 Å (aromatic) or 0.98 Å (methyl) and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N), or 1.5Ueq(C) for the methyl group.

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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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
C7H7IN2O3Z = 2
Mr = 294.05F(000) = 280
Triclinic, P1Dx = 2.163 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.0671 (3) ÅCell parameters from 2061 reflections
b = 8.0739 (4) Åθ = 3.7–27.5°
c = 8.6212 (5) ŵ = 3.52 mm1
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 anode1845 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.7°
ϕ and ω scansh = 910
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1010
Tmin = 0.720, Tmax = 0.902l = 1111
8665 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0279P)2]
where P = (Fo2 + 2Fc2)/3
2061 reflections(Δ/σ)max = 0.001
119 parametersΔρmax = 1.27 e Å3
0 restraintsΔρmin = 0.77 e Å3
Crystal data top
C7H7IN2O3γ = 93.810 (3)°
Mr = 294.05V = 451.55 (4) Å3
Triclinic, P1Z = 2
a = 8.0671 (3) ÅMo Kα radiation
b = 8.0739 (4) ŵ = 3.52 mm1
c = 8.6212 (5) ÅT = 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)
Tmin = 0.720, Tmax = 0.902Rint = 0.039
8665 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.053H-atom parameters constrained
S = 1.00Δρmax = 1.27 e Å3
2061 reflectionsΔρmin = 0.77 e Å3
119 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I20.21628 (2)0.90838 (2)0.66781 (3)0.02135 (8)
O10.7476 (3)0.6384 (3)1.0752 (3)0.0265 (5)
O20.7049 (3)0.3445 (3)0.9016 (3)0.0256 (5)
O60.1721 (3)0.1987 (3)0.2458 (3)0.0194 (4)
N10.0624 (3)0.5013 (4)0.2886 (3)0.0235 (6)
N40.6613 (3)0.4922 (3)0.9212 (3)0.0190 (5)
C10.2056 (4)0.5048 (4)0.4476 (4)0.0151 (6)
C20.2989 (4)0.6607 (4)0.6293 (4)0.0149 (6)
C30.4480 (4)0.6571 (4)0.7856 (4)0.0169 (6)
C40.5038 (4)0.4954 (4)0.7597 (4)0.0151 (6)
C50.4153 (4)0.3347 (4)0.5824 (4)0.0156 (6)
C60.2686 (4)0.3417 (4)0.4282 (4)0.0162 (6)
C610.2159 (4)0.0240 (4)0.2147 (4)0.0224 (6)
H30.51030.76400.90790.020*
H50.45500.22410.56860.019*
H110.02250.60140.29570.028*
H120.00940.39890.17830.028*
H61A0.35030.04050.24870.034*
H61B0.13610.06670.07890.034*
H61C0.19140.02170.29520.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I20.02230 (12)0.01713 (12)0.02269 (12)0.01023 (8)0.00859 (8)0.00921 (9)
O10.0306 (11)0.0176 (11)0.0140 (11)0.0105 (9)0.0000 (9)0.0026 (9)
O20.0318 (11)0.0166 (11)0.0202 (11)0.0142 (9)0.0055 (9)0.0077 (9)
O60.0186 (9)0.0146 (10)0.0142 (10)0.0055 (8)0.0014 (8)0.0037 (8)
N10.0224 (12)0.0182 (13)0.0171 (13)0.0084 (10)0.0008 (10)0.0055 (11)
N40.0206 (12)0.0185 (13)0.0141 (12)0.0070 (10)0.0052 (10)0.0073 (11)
C10.0137 (13)0.0180 (14)0.0155 (14)0.0042 (11)0.0066 (11)0.0099 (12)
C20.0170 (13)0.0107 (13)0.0174 (14)0.0061 (11)0.0081 (11)0.0068 (11)
C30.0184 (13)0.0149 (14)0.0149 (14)0.0035 (11)0.0067 (11)0.0062 (12)
C40.0132 (12)0.0187 (15)0.0088 (13)0.0039 (11)0.0018 (10)0.0059 (11)
C50.0169 (13)0.0154 (14)0.0155 (14)0.0053 (11)0.0071 (11)0.0087 (12)
C60.0156 (13)0.0134 (14)0.0127 (14)0.0020 (11)0.0043 (11)0.0028 (11)
C610.0247 (15)0.0134 (15)0.0168 (15)0.0040 (12)0.0045 (12)0.0021 (12)
Geometric parameters (Å, º) top
C1—N11.356 (3)C4—N41.445 (3)
C1—C21.401 (4)N4—O21.234 (3)
C1—C61.418 (4)N4—O11.242 (3)
N1—H110.88C5—C61.381 (4)
N1—H120.88C5—H50.95
C2—C31.388 (4)C6—O61.363 (3)
C2—I22.100 (3)O6—C611.429 (4)
C3—C41.377 (4)C61—H61A0.98
C3—H30.95C61—H61B0.98
C4—C51.399 (4)C61—H61C0.98
N1—C1—C2124.3 (3)O2—N4—C4119.0 (2)
N1—C1—C6118.0 (3)O1—N4—C4118.6 (2)
C2—C1—C6117.7 (2)C6—C5—C4118.0 (3)
C1—N1—H11120.0C6—C5—H5121.0
C1—N1—H12120.0C4—C5—H5121.0
H11—N1—H12120.0O6—C6—C5124.9 (3)
C3—C2—C1121.6 (3)O6—C6—C1113.5 (2)
C3—C2—I2118.6 (2)C5—C6—C1121.6 (2)
C1—C2—I2119.83 (19)C6—O6—C61117.7 (2)
C4—C3—C2118.6 (3)O6—C61—H61A109.5
C4—C3—H3120.7O6—C61—H61B109.5
C2—C3—H3120.7H61A—C61—H61B109.5
C3—C4—C5122.5 (2)O6—C61—H61C109.5
C3—C4—N4118.8 (2)H61A—C61—H61C109.5
C5—C4—N4118.7 (2)H61B—C61—H61C109.5
O2—N4—O1122.4 (2)
N1—C1—C2—C3178.3 (3)C5—C4—N4—O1175.5 (3)
C6—C1—C2—C30.1 (4)C3—C4—C5—C61.1 (4)
N1—C1—C2—I20.6 (4)N4—C4—C5—C6178.2 (3)
C6—C1—C2—I2179.0 (2)C4—C5—C6—O6178.2 (3)
C1—C2—C3—C40.2 (4)C4—C5—C6—C11.2 (4)
I2—C2—C3—C4179.2 (2)N1—C1—C6—O60.3 (4)
C2—C3—C4—C50.4 (4)C2—C1—C6—O6178.8 (2)
C2—C3—C4—N4178.9 (2)N1—C1—C6—C5179.1 (3)
C3—C4—N4—O2175.9 (3)C2—C1—C6—C50.6 (4)
C5—C4—N4—O24.8 (4)C5—C6—O6—C615.0 (4)
C3—C4—N4—O13.8 (4)C1—C6—O6—C61175.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H11···O1i0.882.363.007 (3)130
N1—H12···O2i0.882.453.028 (3)124
Symmetry code: (i) x1, y, z1.

Experimental details

Crystal data
Chemical formulaC7H7IN2O3
Mr294.05
Crystal system, space groupTriclinic, 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)
V3)451.55 (4)
Z2
Radiation typeMo Kα
µ (mm1)3.52
Crystal size (mm)0.10 × 0.06 × 0.03
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.720, 0.902
No. of measured, independent and
observed [I > 2σ(I)] reflections
8665, 2061, 1845
Rint0.039
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.053, 1.00
No. of reflections2061
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H11···O1i0.882.363.007 (3)130
N1—H12···O2i0.882.453.028 (3)124
Symmetry code: (i) x1, y, z1.
 

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

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First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
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