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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 11| November 2005| Pages o634-o638
doi:10.1107/S0108270105030180

Contrasting three-dimensional framework structures in the isomeric pair 2-iodo-N-(2-nitro­phenyl)­benzamide and N-(2-iodo­phenyl)-2-nitro­benzamide

CROSSMARK_Color_square_no_text.svg
James L. Wardell,a Janet M. S. Skakle,b John N. Lowb and Christopher Glidewellc*

aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 20 September 2005; accepted 21 September 2005; online 11 October 2005)

In 2-iodo-N-(2-nitro­phenyl)­benzamide, C13H9IN2O3, the mol­ecules are linked into a three-dimensional framework structure by a combination of a C—H⋯O hydrogen bond, and iodo–nitro, carbonyl–carbonyl and aromatic π–π stacking inter­actions. In the isomeric compound N-(2-iodo­phenyl)-2-nitro­benzamide, the framework structure is built from N—H⋯O, C—H⋯O and C—H⋯π(arene) hydrogen bonds and an iodo–nitro inter­action.

Comment

The isomeric benzamides 2-iodo-N-(2-nitro­phenyl)­benzamide, (I)[link], and N-(2-iodo­phenyl)-2-nitro­benzamide, (II)[link], offer the possibility of a wide variety of potential inter­molecular inter­actions. These include N—H⋯O and C—H⋯O hydrogen bonds, each with two possible types of acceptor O atoms (amide and nitro), C—H⋯π(arene) hydrogen bonds (again with two distinct acceptor rings), aromatic π–π stacking inter­actions, and two- or three-centre iodo–nitro inter­actions. We have recently reported that the supramol­ecular aggregation of 2-iodo-N-(4-nitro­phenyl)­benzamide, (III), depends on a combination of N—H⋯O(carbon­yl) and C—H⋯O(nitro) hydrogen bonds, together with weak π–π stacking inter­actions (Garden et al., 2005[Garden, S. J., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst. C61, o450-o451.]), and we now report the supramolecular structures for the isomers (I)[link] and (II)[link].

The mol­ecules in (I)[link] and (II)[link] (Figs. 1[link] and 2[link], respectively) adopt conformations which have no inter­nal symmetry, as shown by the leading torsion angles (Table 1[link]). Accordingly, the mol­ecules of (I)[link] and (II)[link] have no internal symmetry, and hence they are chiral. Compound (I)[link] crystallizes in the centrosymmetric space group [P\overline{1}], so that equal numbers of both enantiomers are present in each crystal, but compound (II)[link] crystallizes in the non-centrosymmetric space group P212121; hence, in the absence of any inversion twinning, only one enantiomer is present in a given crystal of compound (II)[link]. The bond lengths and angles show no unusual values.

[Scheme 1]

The supramolecular structures formed by isomers (I)[link] and (II)[link] are both three-dimensional, but they are different not only in their detailed construction but also in the types of direction-specific inter­molecular inter­actions which are active.

In compound (I)[link] (Fig. 1[link]), there is an intra­molecular N—H⋯O hydrogen bond (Table 2[link]), but the N—H bond plays no role in the inter­molecular aggregation. This is instead determined by a combination of a C—H⋯O hydrogen bond, a two-centre iodo–nitro inter­action and two aromatic π–π stacking inter­actions, which combine to generate a three-dimensional framework, the formation of which is readily analysed in terms of three one-dimensional substructures.

For two of the substructures, the basic building block is a hydrogen-bonded dimer. Aryl atom C25 in the mol­ecule at (x, y, z) acts as donor to amide atom O17 in the mol­ecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric R22(14) dimer centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]) (Fig. 3[link]). These dimers are linked into two distinct chains by aromatic π–π stacking inter­actions.

Because of the near planarity of the mol­ecules in compound (I)[link], the C11–C16 ring at (x, y, z) is nearly parallel to the C21–C26 rings in the mol­ecules at (−x, −y, 1 − z) and (−x, 1 − y, 1 − z), with dihedral angles between adjacent planes of only 5.2 (2)°. For the mol­ecules at (x, y, z) and (−x, −y, 1 − z), the corresponding ring-centroid separation is 3.827 (2) Å, with an inter­planar spacing of ca 3.49 Å and a ring offset of ca 1.57 Å. The mol­ecules at (x, y, z) and (−x, −y, 1 − z) are components of the hydrogen-bonded dimers centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]) and (−[{1\over 2}], −[{1\over 2}], [{1\over 2}]), respectively, so that propagation by inversion of these two inter­actions generates a π-stacked chain of rings running parallel to the [110] direction (Fig. 4[link]). For the mol­ecules at (x, y, z) and (−x, 1 − y, 1 − z), which are components of the hydrogen-bonded dimers centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]) and (−[{1\over 2}], [{1\over 2}], [{1\over 2}]), respectively, the ring-centroid separation is 3.808 (2) Å, with an inter­planar separation of ca 3.52 Å and a ring offset of ca 1.45 Å. This inter­action thus generates a π-­stacked chain of rings running parallel to the [100] direction (Fig. 5[link]).

The final substructure depends solely on a two-centre iodo–nitro inter­action, with I12⋯O22i = 3.4101 (16) Å and C12—I12⋯O22i = 159.71 (6)° [symmetry code: (i) x, y, −1 + z], so forming a C(9) chain (Starbuck et al., 1999[Starbuck, J., Norman, N. C. & Orpen, A. G. (1999). New J. Chem. 23, 969-972.]) running parallel to the [001] direction (Fig. 6[link]). The combination of [100], [110] and [001] chains then generates a three-dimensional structure, which is augmented by a carbonyl–carbonyl inter­action of type II (Allen et al., 1998[Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta Cryst. B54, 320-329.]). The carbonyl groups in the mol­ecules at (x, y, z) and (−x, 1 − y, 1 − z) are strictly parallel, with O17⋯C17ii = 2.976 (2) Å and C17—O17⋯C17ii = 92.8 (2)° [symmetry code: (ii) −x, 1 − y, 1 − z].

The mol­ecules of compound (II)[link] (Fig. 2[link]) are linked into a three-dimensional framework structure by a combination of N—H⋯O, C—H⋯O and C—H⋯π(arene) hydrogen bonds (Table 3[link]) and a two-centre iodo–nitro inter­action. The formation of this framework is readily analysed in terms of three one-dimensional substructures. In the first substructure, amide atom N1 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to carbonyl atom O17 in the mol­ecule at (−[{1\over 2}] + y, [{3\over 2}] − y, 1 − z), so forming the C(4) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) motif characteristic of simple amides running parallel to the [100] direction and generated by the 21 screw axis along (x, [{3\over 4}], [{1\over 2}]) (Fig. 7[link]).

The second substructure arises from the co-operative action of two fairly weak inter­actions. Aryl atom C24 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to amide atom O17 in the mol­ecule at (1 − x, −[{1\over 2}] + y, [{3\over 2}] − z), while atom C24 at (1 − x, −[{1\over 2}] + y, [{3\over 2}] − z) in turn acts as donor to atom O17 at (x, 1 + y, z), so forming a C(8) chain running parallel to the [010] direction (Fig. 8[link]). At the same time, atoms I22 at (x, y, z) and O22 at (x, 1 + y, z) form a two-centre iodo–nitro inter­action, with I⋯Oiii = 3.3677 (17) Å and C—I⋯Oiii = 159.71 (6)° [symmetry code: (iii) x, 1 + y, z], so forming a C(9) chain (Starbuck et al., 1999[Starbuck, J., Norman, N. C. & Orpen, A. G. (1999). New J. Chem. 23, 969-972.]). The combination of these two inter­actions then generates a chain of edge-fused R33(19) rings generated by the 21 screw axis along ([{1\over 2}], y, [{3\over 4}]) (Fig. 8[link]).

The third one-dimensional substructure in (II)[link] is built from a single C—H⋯π(arene) hydrogen bond. Aryl atom C23 in the mol­ecule at (x, y, z) acts as donor to the C11–C16 ring in the mol­ecule at ([{1\over 2}] − x, 1 − y, [{1\over 2}] + z), so forming a chain running parallel to the [001] direction and generated by the 21 screw axis along ([{1\over 4}], [{1\over 2}], z) (Fig. 9[link]). The combination of the chains along [100], [010] and [001] suffices to generate a continuous three-dimensional framework.

In conclusion, for the two isomeric title compounds, (I)[link] and (II)[link], the difference between their mol­ecular structures can be regarded as a simple reversal of the amidic function –NH—CO– between (I)[link] and (II)[link], yet they manifest very different ranges of direction-specific inter­molecular inter­actions with consequently very different supramolecular structures.

[Figure 1]
Figure 1
The mol­ecule of compound (I)[link], 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
The mol­ecule of compound (II)[link], 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 3]
Figure 3
Part of the crystal structure of compound (I)[link], showing the formation of a cyclic R22(14) dimer. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of compound (I)[link], showing the formation of a π-stacked chain of hydrogen-bonded dimers along [110]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of compound (I)[link], showing the formation of a π-stacked chain of hydrogen-bonded dimers along [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 6]
Figure 6
Part of the crystal structure of compound (I)[link], showing the formation of an [001] chain built from iodo–nitro inter­actions. For the sake of clarity, H atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, y, −1 + z) and (x, y, 1 + z), respectively.
[Figure 7]
Figure 7
Part of the crystal structure of compound (II)[link], showing the formation of a hydrogen-bonded C(4) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−[{1\over 2}] + y, [{3\over 2}] − y, 1 − z) and ([{1\over 2}] + y, [{3\over 2}] − y, 1 − z), respectively.
[Figure 8]
Figure 8
A stereoview of part of the crystal structure of compound (II)[link], showing the formation of a chain of edge-fused rings along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 9]
Figure 9
Part of the crystal structure of compound (II)[link], showing the formation of a hydrogen-bonded chain along [001]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1\over 2}] − x, 1 − y, [{1\over 2}] + z) and ([{1\over 2}] − x, 1 − y, −[{1\over 2}] + z), respectively.

Experimental

The title amides were obtained by reaction of equimolar mixtures (2 mmol of each) of 2-XC6H4COCl and 2-YC6H4NH2 [for (I)[link], X = I and Y = NO2; for (II)[link], X = NO2 and Y = I] in chloro­form (50 ml). After heating each mixture under reflux for 1 h, the solvent was removed under reduced pressure and the resulting solid residues were recrystallized from ethanol, yielding crystals suitable for single-crystal X-ray diffraction.

Compound (I)[link]

Crystal data

  • C13H9IN2O3

  • Mr = 368.12

  • Triclinic, [P \overline 1]

  • a = 7.2773 (2) Å

  • b = 7.62070 (10) Å

  • c = 11.6821 (3) Å

  • α = 100.248 (2)°

  • β = 107.7770 (10)°

  • γ = 92.529 (2)°

  • V = 603.73 (2) Å3

  • Z = 2

  • Dx = 2.025 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2759 reflections

  • θ = 3.6–27.5°

  • μ = 2.66 mm−1

  • T = 120 (2) K

  • Plate, yellow

  • 0.34 × 0.20 × 0.04 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 = 0.465, Tmax = 0.901

  • 12249 measured reflections

  • 2759 independent reflections

  • 2646 reflections with I > 2σ(I)

  • Rint = 0.023

  • θmax = 27.5°

  • h = −9 → 9

  • k = −9 → 9

  • l = −15 → 15
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.018

  • wR(F2) = 0.045

  • S = 1.07

  • 2759 reflections

  • 172 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0212P)2 + 0.5992P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 1.18 e Å−3

  • Δρmin = −0.65 e Å−3

Table 1
Selected torsion angles (°) for compounds (I)[link] and (II)[link]

  (I)[link] (II)[link]
C11—C17—N1—C21 −168.48 (17) −173.38 (16)
C12—C11—C17—N1 −149.64 (18) 76.1 (2)
C22—C21—N1—C17 147.54 (19) −143.98 (19)
C11—C12—N12—O21   12.0 (3)
C21—C22—N22—O21 16.7 (3)  

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O21 0.88 2.11 2.649 (2) 119
C25—H25⋯O17i 0.95 2.38 3.312 (3) 168
C26—H26⋯O17 0.95 2.34 2.883 (3) 116
Symmetry code: (i) -x+1, -y+1, -z+1.

Compound (II)[link]

Crystal data

  • C13H9IN2O3

  • Mr = 368.12

  • Orthorhombic, P 21 21 21

  • a = 8.8908 (2) Å

  • b = 9.7468 (2) Å

  • c = 15.0112 (2) Å

  • V = 1300.82 (4) Å3

  • Z = 4

  • Dx = 1.880 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2970 reflections

  • θ = 4.1–27.5°

  • μ = 2.47 mm−1

  • T = 120 (2) K

  • Rod, colourless

  • 0.40 × 0.10 × 0.10 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 = 0.439, Tmax = 0.791

  • 18237 measured reflections

  • 2970 independent reflections

  • 2906 reflections with I > 2σ(I)

  • Rint = 0.028

  • θmax = 27.5°

  • h = −10 → 11

  • k = −12 → 12

  • l = −19 → 18
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.017

  • wR(F2) = 0.036

  • S = 1.08

  • 2970 reflections

  • 173 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0148P)2 + 0.3804P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.47 e Å−3

  • Δρmin = −0.49 e Å−3

  • Extinction correction: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.])

  • Extinction coefficient: 0.0129 (4)

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), with 1249 Friedel pairs

  • Flack parameter: −0.001 (13)

Table 3
Hydrogen-bond geometry (Å, °) for (II)[link]

Cg1 is the centroid of the C11–C16 ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O17i 0.88 1.94 2.792 (2) 161
C24—H24⋯O17ii 0.95 2.54 3.321 (3) 140
C23—H23⋯Cg1iii 0.95 2.94 3.846 (2) 160
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) [-x+{\script{1\over 2}}], -y+1, [z+{\script{1\over 2}}].

Crystals of compound (I)[link] are triclinic. The space group P[\overline{1}] was selected and confirmed by the subsequent structure analysis. For compound (II)[link], the space group P212121 was uniquely determined from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). The absolute configuration of the mol­ecules in the crystal of (II)[link] selected for data collection was established by use of the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter, although this configuration has no chemical significance.

For both compounds, data collection: COLLECT (Nonius, 1999[Nonius (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

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270105030180/sk1872sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105030180/sk1872Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105030180/sk1872IIsup3.hkl


Comment top

The isomeric benzamides N-(2-nitrophenyl)-2-iodobenzamide, (I), and N-(2-iodophenyl)-2-nitrobenzamide, (II), offer the possibility of a wide variety of potential intermolecular interactions. These include N—H···O and C—H···O hydrogen bonds, each with two possible types of O acceptor atoms (amide and nitro), C—H···π(arene) hydrogen bonds (again with two distinct acceptor rings), aromatic π–π stacking interactions, and two- or three-centre iodo···nitro interactions. We have recently reported that the supramolecular aggregation of N-(4-nitrophenyl)-2-iodobenzamide, (III), depends on a combination of N—H···O(carbonyl) and C—H···O(nitro) hydrogen bonds, together with weak π–π stacking interactions (Garden et al., 2005), and we now report the supramolecular structures for the isomers (I) and (II).

The molecules in compounds (I) and (II) (Figs. 1 and 2, respectively) adopt conformations which have no internal symmetry, as shown by the leading torsion angles (Table 1). Accordingly, the molecules of compounds (I) and (II) have no internal symmetry, and hence they are chiral. Compound (I) crystallizes in the centrosymmetric space group P1, so that equal numbers of both enantiomers are present in each crystal, but compound (II) crystallizes in the non-centrosymmetric space group P212121; hence, in the absence of any inversion twinning, only one enantiomer is present in a given crystal of compound (II). The bond lengths and angles show no unusual values.

The supramolecular structures formed by the isomers (I) and (II) are both three-dimensional, but they are different not only in their detailed construction but also in the types of direction-specific intermolecular interactions which are active.

In compound (I) (Fig. 1), there is an intramolecular N—H···O hydrogen bond (Table 2), but the N—H bond plays no role in the intermolecular aggregation. This is instead determined by a combination of a C—H···O hydrogen bond, a two-centre iodo···nitro interaction and two aromatic π–π stacking interactions, which combine to generate a three-dimensional framework, the formation of which is readily analysed in terms of three one-dimensional sub-structures.

For two of the sub-structures, the basic building block is a hydrogen-bonded dimer. Aryl atom C25 in the molecule at (x, y, z) acts as donor to amidic atom O17 in the molecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric R22(14) dimer centred at (1/2, 1/2, 1/2) (Fig. 3). These dimers are linked into two distinct chains by aromatic π–π stacking interactions.

Because of the near-planarity of the molecules in compound (I), the C11–C16 ring at (x, y, z) is nearly parallel to the C21–C26 rings in the molecules at (−x, −y, 1 − z) and (−x, 1 − y, 1 − z), with dihedral angles between adjacent planes of only 5.2 (2)°. For the molecules at (x, y, z) and (−x, −y, 1 − z), the corresponding ring-centroid separation is 3.827 (2) Å, with an interplanar spacing of ca 3.49 Å and a ring offset of ca 1.57 Å. The molecules at (x, y, z) and (−x, −y, 1 − z) are components of the hydrogen-bonded dimers centred at (1/2, 1/2, 1/2) and (−1/2, −1/2, 1/2), respectively, so that propagation by inversion of these two interactions generates a π-stacked chain of rings running parallel to the [110] direction (Fig. 4). For the molecules at (x, y, z) and (−x, 1 − y, 1 − z), which are components of the hydrogen-bonded dimers centred at (1/2, 1/2, 1/2) and (−1/2, 1/2, 1/2), respectively, the ring-centroid separation is 3.808 (2) Å, with an interplanar separation of ca 3.52 Å and a ring offset of ca 1.45 Å. This interaction thus generates a π-stacked chain of rings running parallel to the [100] direction (Fig. 5).

The final sub-structure depends solely on a two-centre iodo ···nitro interaction, with I12···O22i 3.4101 (16) Å and C12—I12···O22i 159.71 (6)° [symmetry code: (i) x, y, −1 + z], so forming a C(9) chain (Starbuck et al., 1999) running parallel to the [001] direction (Fig. 6). The combination of [100], [110] and [001] chains then generates a three-dimensional structure, which is augmented by a carbonyl···carbonyl interaction of type (II) (Allen et al., 1998). The carbonyl groups in the molecules at (x, y, z) and (−x, 1 − y, 1 − z) are strictly parallel, with O17···C17ii 2.976 (2) Å and C17—O17···C17ii 92.8 (2)° [symmetry code: (ii) −x, 1 − y, 1 − z].

The molecules of compound (II) (Fig. 2) are linked into a three-dimensional framework structure by a combination of N—H···O, C—H···O and C—H···π(arene) hydrogen bonds (Table 3) and a two-centre iodo···nitro interaction. The formation of this framework is readily analysed in terms of three one-dimensional sub-structures. In the first sub-structure, the amide atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor to carbonyl atom O17 in the molecule at (−1/2 + y, 3/2 − y, 1 − z), so forming the C(4) (Bernstein et al., 1995) motif characteristic of simple amides running parallel to the [100] direction and generated by the 21 screw axis along (x, 3/4, 1/2) (Fig. 7).

The second sub-structure arises from the cooperative action of two fairly weak interactions. Aryl atom C24 in the molecule at (x, y, z) acts as hydrogen-bond donor to amide atom O17 in the molecule at (1 − x, −1/2 + y, 3/2 − z), while atom C24 at (1 − x, −1/2 + y, 3/2 − z) in turn acts as donor to atom O17 at (x, 1 + y, z), so forming a C(8) chain running parallel to the [010] direction (Fig. N3 Please supply this figure). At the same time, atoms I22 at (x, y, z) and O22 at (x, 1 + y, z) form a two-centre iodo ···nitro interaction, with I···Oiii 3.3677 (17) Å and C—I···Oiii 159.71 (6)° [symmetry code: (iii) x, 1 + y, z], so forming a C(9) chain (Starbuck et al., 1999). The combination of these two interactions then generates a chain of edge-fused R33(19) rings generated by the 21 screw axis along (1/2, y, 3/4) (Fig. 8).

The third one-dimensional sub-structure in (II) is built from a single C—H···π(arene) hydrogen bond. Aryl atom C23 in the molecule at (x, y, z) acts as donor to the C11–C16 ring in the molecule at (1/2 − x, 1 − y, 1/2 + z), so forming a chain running parallel to the [001] direction and generated by the 21 screw axis along (1/4, 1/2, z) (Fig. 9). The combination of the chains along [100], [010] and [001] suffices to generate a continuous three-dimensional framework.

In conclusion, for the two isomeric compounds, (I) and (II), the difference between their molecular structures can be regarded as a simple reversal of the amidic function –NH—CO– between (I) and (II), yet they manifest very different ranges of direction-specific intermolecular interactions with consequently very different supramolecular structures.

Experimental top

The amides were obtained from reaction of equimolar mixtures (2 mmol of each) of 2-XC6H4COCl and 2-YC6H4NH2 [for (I), X = I and Y = NO2; for (II), X = NO2 and Y = I] in chloroform (50 ml). After heating each mixture under reflux for 1 h, the solvent was removed under reduced pressure and the resulting solid residues were recrystallized from ethanol, to yield crystals suitable for single-crystal X-ray diffraction.

Refinement top

Crystals of compound (I) are triclinic. The space group P1 was selected, and confirmed by the subsequent structure analysis. For compound (II), the space group P212121 was uniquely determined from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). The absolute configuration of the molecules in the crystal of (II) selected for data collection was established by use of the Flack parameter (Flack, 1983), although this configuration has no chemical significance.

Computing details top

For both compounds, data collection: COLLECT (Nonius, 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 compound (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. The molecule of compound (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.
[Figure 3] Fig. 3. Part of the crystal structure of compound (I), showing the formation of a cyclic R22(14) dimer. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a π-stacked chain of hydrogen-bonded dimers along [110]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of compound (I), showing the formation of a π-stacked chain of hydrogen-bonded dimers along [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 6] Fig. 6. Part of the crystal structure of compound (I), showing the formation of an [001] chain built from iodo···nitro interactions. For the sake of clarity, H atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, y, −1 + z) and (x, y, 1 + z), respectively.
[Figure 7] Fig. 7. Part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded C(4) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1/2 + y, 3/2 − y, 1 − z) and (1/2 + y, 3/2 − y, 1 − z), respectively.
[Figure 8] Fig. 8. A stereoview of part of the crystal structure of compound (II), showing the formation of a chain of edge-fused rings along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 9] Fig. 9. Part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded chain along [001]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 − x, 1 − y, 1/2 + z) and (1/2 − x, 1 − y, −1/2 + z), respectively.
(I) N-(2-nitrophenyl)-2-iodobenzamide top
Crystal data top
C13H9IN2O3Z = 2
Mr = 368.12F(000) = 356
Triclinic, P1Dx = 2.025 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2773 (2) ÅCell parameters from 2759 reflections
b = 7.6207 (1) Åθ = 3.6–27.5°
c = 11.6821 (3) ŵ = 2.66 mm−1
α = 100.248 (2)°T = 120 K
β = 107.777 (1)°Plate, yellow
γ = 92.529 (2)°0.34 × 0.20 × 0.04 mm
V = 603.73 (2) Å3
Data collection top
Nonius KappaCCD area-detector
diffractometer		2759 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode2646 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.6°
ϕ and ω scansh = −9→9
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −9→9
Tmin = 0.465, Tmax = 0.901l = −15→15
12249 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)] = 0.018Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.045H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0212P)2 + 0.5992P]
where P = (Fo2 + 2Fc2)/3
2759 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 1.18 e Å−3
0 restraintsΔρmin = −0.65 e Å−3
Crystal data top
C13H9IN2O3γ = 92.529 (2)°
Mr = 368.12V = 603.73 (2) Å3
Triclinic, P1Z = 2
a = 7.2773 (2) ÅMo Kα radiation
b = 7.6207 (1) ŵ = 2.66 mm−1
c = 11.6821 (3) ÅT = 120 K
α = 100.248 (2)°0.34 × 0.20 × 0.04 mm
β = 107.777 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer		2759 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2646 reflections with I > 2σ(I)
Tmin = 0.465, Tmax = 0.901Rint = 0.023
12249 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0180 restraints
wR(F2) = 0.045H-atom parameters constrained
S = 1.07Δρmax = 1.18 e Å−3
2759 reflectionsΔρmin = −0.65 e Å−3
172 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I12−0.108891 (17)0.241979 (16)0.116436 (11)0.01584 (5)
O170.0865 (2)0.40677 (19)0.39863 (13)0.0160 (3)
O21−0.0404 (2)0.1305 (2)0.71175 (14)0.0202 (3)
O220.1146 (2)0.2554 (2)0.90012 (15)0.0275 (4)
N10.0731 (2)0.2290 (2)0.53551 (15)0.0126 (3)
N220.1022 (2)0.2218 (2)0.79120 (16)0.0153 (3)
C11−0.2053 (3)0.2139 (2)0.35607 (18)0.0121 (4)
C12−0.2769 (3)0.1909 (2)0.22784 (18)0.0120 (4)
C13−0.4689 (3)0.1214 (3)0.16427 (19)0.0150 (4)
C14−0.5920 (3)0.0720 (3)0.2264 (2)0.0161 (4)
C15−0.5246 (3)0.0964 (3)0.35323 (19)0.0156 (4)
C16−0.3340 (3)0.1684 (3)0.41702 (19)0.0136 (4)
C17−0.0017 (3)0.2940 (2)0.42967 (18)0.0121 (4)
C210.2438 (3)0.2985 (2)0.63227 (18)0.0124 (4)
C220.2627 (3)0.2908 (2)0.75486 (18)0.0130 (4)
C230.4352 (3)0.3532 (3)0.85005 (19)0.0159 (4)
C240.5930 (3)0.4266 (3)0.8256 (2)0.0181 (4)
C250.5763 (3)0.4384 (3)0.70539 (19)0.0161 (4)
C260.4050 (3)0.3756 (3)0.61060 (18)0.0137 (4)
H10.00730.13460.54320.015*
H13−0.51620.10760.07750.018*
H14−0.72150.02180.18210.019*
H15−0.60820.06410.39640.019*
H16−0.28980.18720.50410.016*
H230.44440.34530.93180.019*
H240.71120.46830.89000.022*
H250.68350.49010.68800.019*
H260.39690.38520.52930.016*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I120.01425 (8)0.02280 (8)0.01220 (8)0.00112 (5)0.00549 (5)0.00590 (5)
O170.0155 (7)0.0187 (7)0.0145 (7)−0.0031 (5)0.0055 (6)0.0049 (6)
O210.0141 (7)0.0265 (8)0.0192 (8)−0.0056 (6)0.0032 (6)0.0080 (6)
O220.0314 (10)0.0359 (10)0.0168 (8)−0.0077 (7)0.0131 (7)0.0027 (7)
N10.0110 (8)0.0131 (7)0.0125 (8)−0.0031 (6)0.0023 (6)0.0032 (6)
N220.0166 (8)0.0167 (8)0.0149 (9)0.0011 (6)0.0068 (7)0.0058 (7)
C110.0116 (9)0.0106 (8)0.0138 (9)0.0013 (7)0.0037 (7)0.0022 (7)
C120.0127 (9)0.0116 (8)0.0143 (10)0.0032 (7)0.0066 (7)0.0045 (7)
C130.0145 (9)0.0174 (9)0.0118 (10)0.0025 (7)0.0023 (8)0.0027 (7)
C140.0101 (9)0.0155 (9)0.0209 (11)0.0006 (7)0.0032 (8)0.0019 (8)
C150.0133 (9)0.0157 (9)0.0201 (10)0.0009 (7)0.0081 (8)0.0051 (8)
C160.0143 (9)0.0151 (9)0.0125 (9)0.0014 (7)0.0052 (8)0.0040 (7)
C170.0122 (9)0.0127 (8)0.0116 (9)0.0016 (7)0.0052 (7)0.0005 (7)
C210.0151 (9)0.0097 (8)0.0117 (9)0.0008 (7)0.0045 (8)0.0005 (7)
C220.0133 (9)0.0109 (8)0.0156 (10)0.0007 (7)0.0053 (8)0.0036 (7)
C230.0181 (10)0.0165 (9)0.0124 (10)0.0007 (7)0.0037 (8)0.0035 (7)
C240.0158 (10)0.0172 (9)0.0159 (10)−0.0003 (7)−0.0017 (8)0.0021 (8)
C250.0132 (9)0.0163 (9)0.0202 (11)−0.0005 (7)0.0074 (8)0.0038 (8)
C260.0137 (9)0.0158 (9)0.0127 (9)0.0006 (7)0.0059 (8)0.0030 (7)
Geometric parameters (Å, º) top
C11—C121.403 (3)N1—H10.8797
C11—C161.404 (3)C21—C261.399 (3)
C11—C171.504 (3)C21—C221.409 (3)
C12—C131.395 (3)C22—C231.395 (3)
C12—I122.1097 (18)C22—N221.466 (2)
C13—C141.391 (3)N22—O221.227 (2)
C13—H130.95N22—O211.241 (2)
C14—C151.386 (3)C23—C241.383 (3)
C14—H140.95C23—H230.95
C15—C161.392 (3)C24—C251.391 (3)
C15—H150.95C24—H240.95
C16—H160.95C25—C261.388 (3)
C17—O171.219 (2)C25—H250.95
C17—N11.379 (2)C26—H260.95
N1—C211.405 (2)
C12—C11—C16117.79 (17)C21—N1—H1116.8
C12—C11—C17122.62 (17)C26—C21—N1121.25 (18)
C16—C11—C17119.50 (17)C26—C21—C22116.89 (18)
C13—C12—C11120.36 (17)N1—C21—C22121.84 (17)
C13—C12—I12115.02 (14)C23—C22—C21121.67 (18)
C11—C12—I12124.54 (14)C23—C22—N22115.78 (17)
C14—C13—C12120.77 (19)C21—C22—N22122.53 (17)
C14—C13—H13119.6O22—N22—O21122.13 (17)
C12—C13—H13119.6O22—N22—C22118.47 (17)
C15—C14—C13119.65 (18)O21—N22—C22119.39 (17)
C15—C14—H14120.2C24—C23—C22120.13 (19)
C13—C14—H14120.2C24—C23—H23119.9
C14—C15—C16119.66 (18)C22—C23—H23119.9
C14—C15—H15120.2C23—C24—C25119.09 (19)
C16—C15—H15120.2C23—C24—H24120.5
C15—C16—C11121.71 (19)C25—C24—H24120.5
C15—C16—H16119.1C26—C25—C24120.81 (18)
C11—C16—H16119.1C26—C25—H25119.6
O17—C17—N1123.77 (18)C24—C25—H25119.6
O17—C17—C11122.80 (18)C25—C26—C21121.40 (18)
N1—C17—C11113.42 (16)C25—C26—H26119.3
C17—N1—C21126.50 (16)C21—C26—H26119.3
C17—N1—H1116.7
C16—C11—C12—C13−1.3 (3)C17—N1—C21—C26−33.8 (3)
C17—C11—C12—C13−177.90 (17)C17—N1—C21—C22147.54 (19)
C16—C11—C12—I12−177.89 (13)C26—C21—C22—C23−1.4 (3)
C17—C11—C12—I125.6 (3)N1—C21—C22—C23177.30 (18)
C11—C12—C13—C14−0.6 (3)C26—C21—C22—N22176.85 (17)
I12—C12—C13—C14176.22 (15)N1—C21—C22—N22−4.4 (3)
C12—C13—C14—C151.7 (3)C23—C22—N22—O2214.4 (3)
C13—C14—C15—C16−0.6 (3)C21—C22—N22—O22−163.95 (18)
C14—C15—C16—C11−1.4 (3)C23—C22—N22—O21−164.97 (18)
C12—C11—C16—C152.4 (3)C21—C22—N22—O2116.7 (3)
C17—C11—C16—C15179.06 (17)C21—C22—C23—C240.6 (3)
C12—C11—C17—O1731.2 (3)N22—C22—C23—C24−177.80 (18)
C16—C11—C17—O17−145.32 (19)C22—C23—C24—C250.6 (3)
C12—C11—C17—N1−149.63 (18)C23—C24—C25—C26−0.8 (3)
C16—C11—C17—N133.9 (2)C24—C25—C26—C21−0.1 (3)
O17—C17—N1—C2110.7 (3)N1—C21—C26—C25−177.58 (18)
C11—C17—N1—C21−168.48 (17)C22—C21—C26—C251.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O210.882.112.649 (2)119
C25—H25···O17i0.952.383.312 (3)168
C26—H26···O170.952.342.883 (3)116
Symmetry code: (i) −x+1, −y+1, −z+1.
(II) N-(2-iodophenyl)-2-nitrobenzamide top
Crystal data top
C13H9IN2O3F(000) = 712
Mr = 368.12Dx = 1.880 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2970 reflections
a = 8.8908 (2) Åθ = 4.1–27.5°
b = 9.7468 (2) ŵ = 2.47 mm−1
c = 15.0112 (2) ÅT = 120 K
V = 1300.82 (4) Å3Rod, colourless
Z = 40.40 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		2970 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode2906 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 4.1°
ϕ and ω scansh = −10→11
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −12→12
Tmin = 0.439, Tmax = 0.791l = −19→18
18237 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.017 w = 1/[σ2(Fo2) + (0.0148P)2 + 0.3804P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.036(Δ/σ)max = 0.001
S = 1.08Δρmax = 0.47 e Å−3
2970 reflectionsΔρmin = −0.49 e Å−3
173 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0129 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with 1249 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: −0.001 (13)
Crystal data top
C13H9IN2O3V = 1300.82 (4) Å3
Mr = 368.12Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.8908 (2) ŵ = 2.47 mm−1
b = 9.7468 (2) ÅT = 120 K
c = 15.0112 (2) Å0.40 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		2970 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2906 reflections with I > 2σ(I)
Tmin = 0.439, Tmax = 0.791Rint = 0.028
18237 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.017H-atom parameters constrained
wR(F2) = 0.036Δρmax = 0.47 e Å−3
S = 1.08Δρmin = −0.49 e Å−3
2970 reflectionsAbsolute structure: Flack (1983), with 1249 Friedel pairs
173 parametersAbsolute structure parameter: −0.001 (13)
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I220.234667 (15)0.361146 (12)0.554690 (8)0.02089 (6)
O170.58838 (14)0.78158 (14)0.54509 (9)0.0166 (3)
O210.29408 (17)0.96800 (15)0.54663 (10)0.0246 (3)
O220.14921 (17)1.06565 (17)0.45001 (12)0.0343 (4)
N10.35996 (17)0.67587 (16)0.54408 (10)0.0130 (3)
N120.2527 (2)0.98893 (15)0.46979 (12)0.0200 (3)
C110.4340 (2)0.8130 (2)0.41738 (12)0.0130 (4)
C120.3341 (2)0.9186 (2)0.39740 (13)0.0166 (4)
C130.3090 (3)0.9629 (2)0.31086 (14)0.0219 (5)
C140.3884 (3)0.9028 (2)0.24173 (14)0.0244 (5)
C150.4920 (2)0.8002 (2)0.25987 (14)0.0212 (4)
C160.5139 (2)0.7555 (2)0.34644 (14)0.0174 (4)
C170.4662 (2)0.7582 (2)0.50910 (14)0.0125 (4)
C210.36400 (19)0.6263 (2)0.63295 (12)0.0130 (4)
C220.3135 (2)0.49537 (19)0.65383 (13)0.0143 (4)
C230.3134 (2)0.4499 (2)0.74139 (13)0.0185 (4)
C240.3654 (2)0.5342 (2)0.80897 (13)0.0212 (4)
C250.4144 (2)0.6655 (2)0.78910 (13)0.0189 (4)
C260.4131 (2)0.7119 (2)0.70196 (13)0.0159 (4)
H10.27200.66940.51760.016*
H130.23831.03370.29910.026*
H140.37180.93180.18210.029*
H150.54820.76040.21270.025*
H160.58450.68450.35780.021*
H230.27750.36050.75510.022*
H240.36750.50200.86870.025*
H250.44890.72400.83540.023*
H260.44590.80250.68890.019*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I220.03035 (8)0.01559 (7)0.01674 (8)−0.00500 (5)−0.00435 (5)0.00018 (5)
O170.0119 (6)0.0231 (8)0.0147 (7)−0.0012 (5)−0.0002 (6)0.0002 (6)
O210.0311 (8)0.0233 (7)0.0192 (8)0.0067 (6)0.0023 (7)−0.0012 (6)
O220.0295 (8)0.0306 (9)0.0429 (10)0.0162 (7)−0.0122 (8)−0.0087 (8)
N10.0123 (7)0.0150 (8)0.0119 (8)−0.0013 (6)−0.0024 (6)0.0014 (6)
N120.0185 (8)0.0128 (7)0.0288 (9)−0.0002 (7)−0.0023 (7)−0.0013 (6)
C110.0125 (9)0.0131 (9)0.0136 (10)−0.0049 (7)0.0000 (7)0.0011 (8)
C120.0174 (9)0.0123 (9)0.0201 (10)−0.0039 (8)−0.0018 (8)0.0005 (8)
C130.0274 (11)0.0136 (9)0.0246 (11)−0.0029 (8)−0.0083 (9)0.0073 (8)
C140.0347 (12)0.0229 (11)0.0156 (10)−0.0110 (9)−0.0058 (9)0.0057 (9)
C150.0238 (11)0.0268 (11)0.0131 (10)−0.0073 (9)0.0022 (8)−0.0026 (9)
C160.0148 (10)0.0190 (10)0.0183 (11)−0.0013 (8)−0.0015 (8)−0.0012 (9)
C170.0121 (9)0.0108 (8)0.0145 (10)0.0012 (7)0.0023 (7)−0.0007 (8)
C210.0113 (8)0.0145 (9)0.0133 (9)0.0026 (8)0.0010 (6)0.0018 (8)
C220.0147 (9)0.0150 (9)0.0133 (10)0.0010 (7)−0.0008 (7)−0.0022 (8)
C230.0217 (10)0.0169 (10)0.0170 (10)0.0009 (8)0.0007 (8)0.0042 (8)
C240.0250 (11)0.0263 (11)0.0122 (10)0.0044 (9)0.0013 (8)0.0042 (8)
C250.0206 (10)0.0203 (11)0.0156 (10)0.0010 (8)−0.0022 (8)−0.0044 (8)
C260.0151 (10)0.0154 (10)0.0172 (10)−0.0009 (8)0.0006 (8)−0.0007 (8)
Geometric parameters (Å, º) top
C11—C121.393 (3)N1—C211.419 (2)
C11—C161.397 (3)N1—H10.8799
C11—C171.504 (3)C17—O171.234 (2)
C12—C131.387 (3)C21—C221.388 (3)
C12—N121.474 (3)C21—C261.400 (3)
N12—O221.222 (2)C22—C231.387 (3)
N12—O211.228 (2)C22—I222.1019 (19)
C13—C141.385 (3)C23—C241.385 (3)
C13—H130.95C23—H230.95
C14—C151.387 (3)C24—C251.385 (3)
C14—H140.95C24—H240.95
C15—C161.384 (3)C25—C261.384 (3)
C15—H150.95C25—H250.95
C16—H160.95C26—H260.95
N1—C171.346 (3)
C12—C11—C16117.16 (18)C21—N1—H1115.1
C12—C11—C17125.52 (17)O17—C17—N1123.84 (19)
C16—C11—C17117.30 (17)O17—C17—C11120.15 (18)
C13—C12—C11122.28 (19)N1—C17—C11115.81 (17)
C13—C12—N12117.84 (18)C22—C21—C26118.79 (17)
C11—C12—N12119.87 (17)C22—C21—N1121.12 (17)
O22—N12—O21123.74 (18)C26—C21—N1120.03 (17)
O22—N12—C12118.34 (17)C23—C22—C21120.51 (18)
O21—N12—C12117.91 (16)C23—C22—I22118.15 (14)
C14—C13—C12119.3 (2)C21—C22—I22121.33 (14)
C14—C13—H13120.4C24—C23—C22120.29 (18)
C12—C13—H13120.4C24—C23—H23119.9
C13—C14—C15119.8 (2)C22—C23—H23119.9
C13—C14—H14120.1C25—C24—C23119.71 (19)
C15—C14—H14120.1C25—C24—H24120.1
C16—C15—C14120.3 (2)C23—C24—H24120.1
C16—C15—H15119.8C26—C25—C24120.19 (19)
C14—C15—H15119.8C26—C25—H25119.9
C15—C16—C11121.20 (19)C24—C25—H25119.9
C15—C16—H16119.4C25—C26—C21120.48 (19)
C11—C16—H16119.4C25—C26—H26119.8
C17—N1—C21123.49 (16)C21—C26—H26119.8
C17—N1—H1119.3
C16—C11—C12—C132.4 (3)C12—C11—C17—O17−108.8 (2)
C17—C11—C12—C13−179.34 (19)C16—C11—C17—O1769.4 (3)
C16—C11—C12—N12−176.55 (17)C12—C11—C17—N176.1 (2)
C17—C11—C12—N121.7 (3)C16—C11—C17—N1−105.6 (2)
C13—C12—N12—O2212.3 (3)C17—N1—C21—C22−143.98 (19)
C11—C12—N12—O22−168.73 (18)C17—N1—C21—C2638.9 (3)
C13—C12—N12—O21−166.94 (17)C26—C21—C22—C23−0.7 (3)
C11—C12—N12—O2112.0 (3)N1—C21—C22—C23−177.83 (17)
C11—C12—C13—C14−1.6 (3)C26—C21—C22—I22179.06 (14)
N12—C12—C13—C14177.37 (18)N1—C21—C22—I221.9 (2)
C12—C13—C14—C15−0.4 (3)C21—C22—C23—C24−0.8 (3)
C13—C14—C15—C161.5 (3)I22—C22—C23—C24179.49 (16)
C14—C15—C16—C11−0.6 (3)C22—C23—C24—C251.5 (3)
C12—C11—C16—C15−1.3 (3)C23—C24—C25—C26−0.8 (3)
C17—C11—C16—C15−179.69 (19)C24—C25—C26—C21−0.7 (3)
C21—N1—C17—O1711.8 (3)C22—C21—C26—C251.4 (3)
C21—N1—C17—C11−173.38 (16)N1—C21—C26—C25178.57 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O17i0.881.942.792 (2)161
C24—H24···O17ii0.952.543.321 (3)140
C23—H23···Cg1iii0.952.943.846 (2)160
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1/2, −y+1, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H9IN2O3C13H9IN2O3
Mr368.12368.12
Crystal system, space groupTriclinic, P1Orthorhombic, P212121
Temperature (K)120120
a, b, c (Å)7.2773 (2), 7.6207 (1), 11.6821 (3)8.8908 (2), 9.7468 (2), 15.0112 (2)
α, β, γ (°)100.248 (2), 107.777 (1), 92.529 (2)90, 90, 90
V (Å3)603.73 (2)1300.82 (4)
Z24
Radiation typeMo KαMo Kα
µ (mm−1)2.662.47
Crystal size (mm)0.34 × 0.20 × 0.040.40 × 0.10 × 0.10
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer		Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.465, 0.9010.439, 0.791
No. of measured, independent and
observed [I > 2σ(I)] reflections		12249, 2759, 2646 18237, 2970, 2906
Rint0.0230.028
(sin θ/λ)max (Å−1)0.6500.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.045, 1.07 0.017, 0.036, 1.08
No. of reflections27592970
No. of parameters172173
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.18, −0.650.47, −0.49
Absolute structure?Flack (1983), with 1249 Friedel pairs
Absolute structure parameter?−0.001 (13)

Computer programs: COLLECT (Nonius, 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) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O210.882.112.649 (2)119
C25—H25···O17i0.952.383.312 (3)168
C26—H26···O170.952.342.883 (3)116
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O17i0.881.942.792 (2)161
C24—H24···O17ii0.952.543.321 (3)140
C23—H23···Cg1iii0.952.943.846 (2)160
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1/2, −y+1, z+1/2.
Selected torsion angles (°) for compounds (I) and (II) top
Parameter(I)(II)
C11-C17-N1-C21-168.48 (17)-173.38 (16)
C12-C11-C17-N1-149.64 (18)76.1 (2)
C22-C21-N1-C17147.54 (19)-143.98 (19)
C11-C12-N12-O2112.0 (3)
C21-C22-N22-O2116.7 (3)
 

Acknowledgements

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

References

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 First citationOtwinowski, 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
 First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
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ISSN: 2053-2296
Volume 61| Part 11| November 2005| Pages o634-o638
doi:10.1107/S0108270105030180
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