Isomeric iodo-N-(nitro­benzyl)anilines: interplay of hard and soft hydrogen bonds, iodo⋯nitro interactions and aromatic π⋯π stacking interactions

Molecules of 2-iodo-N-(4-nitrobenzyl)aniline, 4-O₂NC₆H₄CH₂NHC₆H₄I-2′ (1) are linked into chains by C—H⋯O hydrogen bonds. In the isomeric compound 3-iodo-N-(4-nitrobenzyl)aniline (2) a combination of N—H⋯O and C—H⋯O hydrogen bonds and iodo⋯nitro and aromatic π⋯π stacking interactions links the molecules into a three-dimensional framework structure. The two-dimensional supramolecular structure of 4-iodo-N-(4-nitrobenzyl)aniline (6) is built from a combination of C—H⋯O and N—H⋯π(arene) hydrogen bonds and aromatic π⋯π stacking interactions. 2-Iodo-N-(2-nitrobenzyl)aniline (7) crystallizes with two molecules in the asymmetric unit and these molecules are linked into ladders by a combination of N—H⋯O and C—H⋯O hydrogen bonds and iodo⋯nitro and aromatic π⋯π stacking interactions. Comparisons are made between the supramolecular structures of these compounds and those of other isomers, in terms both of the types of direction-specific intermolecular interactions exhibited and the dimensionality of the resulting supramolecular structures.

1. Introduction

As part of a general study of the interplay of hydrogen bonds, iodo⋯nitro interactions and aromatic π⋯π stacking interactions in aromatic systems containing both iodo and nitro substituents, we have recently reported the molecular and supramolecular structures of a range of diaryl species [see (I)] containing a variety of X spacer units, including arenesulfon­amides (A) and (B) (Kelly et al., 2002) and Schiff-base imines (C) (Wardell et al., 2002) and (D) (Glidewell, Howie et al., 2002), together with some benzylanilines (E) (Glidewell, Low et al., 2002).

In the case of the Schiff-base imines of type (D), we were able to study the supramolecular aggregation modes in eight of the possible nine isomers (Glidewell, Howie et al., 2002), although the structure of the 4,4′-isomer, which crystallizes with Z′ = 2 in space group Fdd2, proved to be elusive because of the intractable disorder. In this series the interplay of the various weak intermolecular interactions is such that neither the supramolecular structure nor even the range of interactions involved can readily be predicted for any single example from a detailed knowledge of all the rest of the series. With this in mind, we have now expanded our preliminary study (Glidewell, Low et al., 2002) of the benzylanilines (E) to incorporate a total of six isomers of this series, (1), (2) and (4)–(7) [see (II)].

2. Experimental

2.1. Synthesis

Nitrobenzylidene-iodoanilines were prepared as previously described (Glidewell, Howie et al., 2002) and subsequently reduced using a fivefold molar excess of sodium borohydride in refluxing methanol. After work-up, crystals of (1), (2), (6) and (7) suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in ethanol. Compound (8) is an oil at ambient temperature and we have not been able to induce crystallization, even at reduced temperatures: (3) and (4) are solids at ambient temperature but, despite repeated efforts, we have so far been unable to obtain any crystals of either compound which are suitable for single-crystal X-ray diffraction.

2.2. Data collection, structure solution and refinement

Diffraction data for (1), (2), (6) and (7) were collected at 120 (2) K using a Nonius Kappa-CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Other details of the cell data, data collection and refinement are summarized in Table 1, together with details of the software employed (Ferguson, 1999; Nonius, 1997; Otwinowski & Minor, 1997; Sheldrick, 1997a,b; McArdle, 2003).¹

Table 1
Experimental details

	(1)	(2)	(6)	(7)
Crystal data
Chemical formula	C13H11IN2O2	C13H11IN2O2	C13H11IN2O2	C13H11IN2O2
Mr	354.14	354.14	354.14	354.14
Cell setting, space group	Monoclinic, P21/c	Orthorhombic, P212121	Monoclinic, P21/c	Triclinic, P
a, b, c (Å)	16.1564 (6), 9.3589 (3), 8.3326 (3)	7.0966 (2), 12.5908 (4), 13.8360 (6)	21.2778 (15), 8.1809 (5), 7.2793 (4)	8.16850 (10), 10.8834 (2), 15.4372 (2)
α, β, γ (°)	90.00, 96.3330 (10), 90.00	90.00, 90.00, 90.00	90.00, 94.316 (2), 90.00	76.9219 (9), 80.0727 (7), 74.2167 (7)
V (Å^3)	1252.25 (8)	1236.27 (8)	1263.53 (14)	1277.36 (3)
Z	4	4	4	4
Dx (Mg m^−3)	1.878	1.903	1.862	1.841
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	2850	2783	2785	5760
θ range (°)	3.3–27.5	2.9–27.5	3.1–27.5	3.1–27.5
μ (mm^−1)	2.55	2.59	2.53	2.50
Temperature (K)	120 (2)	120 (2)	120 (2)	120 (2)
Crystal form, colour	Block, red	Needle, orange	Needle, yellow	Block, orange
Crystal size (mm)	0.32 × 0.22 × 0.15	0.38 × 0.05 × 0.03	0.48 × 0.04 × 0.02	0.22 × 0.18 × 0.12
Data collection
Diffractometer	Kappa-CCD	Kappa-CCD	Kappa-CCD	Kappa-CCD
Data collection method	φ scans, and ω scans with κ offsets	φ scans, and ω scans with κ offsets	φ scans, and ω scans with κ offsets	φ scans, and ω scans with κ offsets
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin	0.496	0.440	0.377	0.597
Tmax	0.682	0.927	0.951	0.738
No. of measured, independent and observed reflections	8013, 2850, 2641	9541, 2783, 2437	12 705, 2785, 1934	5760, 5760, 5317
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.050	0.050	0.064	0.046
θmax (°)	27.5	27.5	27.5	27.5
Range of h, k, l	−20 → h → 20	−8 → h → 9	−27 → h → 27	−10 → h → 10
	−11 → k → 12	−16 → k → 16	−10 → k → 10	−14 → k → 13
	−7 → l → 10	−15 → l → 17	−9 → l → 9	−20 → l → 20
Refinement
Refinement on	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.028, 0.067, 1.08	0.030, 0.050, 1.01	0.035, 0.065, 1.00	0.038, 0.106, 1.14
No. of reflections	2850	2783	2785	5760
No. of parameters	163	163	163	325
H-atom treatment	Constrained to parent site	Constrained to parent site	Constrained to parent site	Constrained to parent site
Weighting scheme	= 1/[σ^2(Fo^2) + (0.0212P)^2 + 2.0006P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0137P)^2], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0209P)^2], where P = (Fo^2 + 2F^c2)/3	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 2.2937P], where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	0.001	0.001	0.001	0.003
Δρmax, Δρmin (e Å^−3)	1.10, −0.74	0.54, −0.61	1.13, −0.60	0.71, −1.65
Absolute structure	–	Flack (1983), 1191 Friedel pairs	–	–
Flack parameter	–	−0.01 (2)	–	–
Computer programs used : Kappa-CCD server software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997b), OSCAIL (McArdle, 2003), SHELXL97 (Sheldrick, 1997a), PLATON (Spek, 2003), PRPKAPPA (Ferguson, 1999).

For (1) and (6) the space group P2₁/c was uniquely assigned from the systematic absences: likewise, the space group P2₁2₁2₁ was uniquely assigned for (2). Compound (7) is triclinic, and the space group was selected and confirmed by the subsequent analysis. The structures were solved by direct methods and refined with all data on F². A weighting scheme based upon P = [F_o² + 2F_c²]/3 was employed in order to reduce statistical bias (Wilson, 1976). All H atoms were located from difference maps and they were included in the refinements as riding atoms with the bond distances C—H 0.95 (aromatic) or 0.99 Å (CH₂) and N—H 0.88 Å. The absolute configuration of (2) in the crystal selected for study was established by the use of the Flack parameter (Flack, 1983), whose final value was −0.01 (2) with 1191 Friedel pairs present.

Supramolecular analyses were made and the diagrams were prepared with the aid of PLATON (Spek, 2003). Details of molecular conformations are given in Table 2. Details of hydrogen-bond dimensions and short intramolecular contacts, and iodo⋯nitro interactions are given in Tables 3 and 4. Figs. 1–13 show the molecular components, with the atom-labelling schemes, and aspects of the supramolecular structures.

Table 2
Selected torsional angles (°)

C11—C17—N1—C21	C12—C11—C17—N1	C17—N1—C21—C22	C—C—N—O11
(1)
79.3 (3)	37.1 (4)	165.7 (2)	−9.2 (5)^i
(2)
−176.0 (3)	−175.9 (3)	17.7 (6)	4.2 (5)^i
(4)†
−84.4 (3)	−167.5 (2)	162.8 (2)	−0.9 (3)^ii
(5)†
63.7 (3)	45.5 (3)	18.2 (3)	−169.3 (2)^ii
(6)
87.8 (4)	43.3 (4)	−16.5 (5)	−5.8 (5)^ii
(7) Molecule 1‡
86.5 (4)	174.7 (3)	175.2 (3)	14.5 (5)^iii
(7) molecule 2‡
−81.6 (4)	166.4 (3)	−168.2 (3)	36.5 (4)^iv
(i) C13—C14—N14—O11; (ii) C12—C13—N13—O11; (iii) C11—C12—N12—O11; (iv) C31—C32—N32—O31

†Atoms labelled as for (1), (2), (6) and (7): for the original labelling scheme see Glidewell, Low et al. (2002).
‡For the atom labels in the two independent molecules, see Fig. 11.

Table 3
Parameters (Å, °) for hydrogen bonds and short intramolecular contacts

D—H⋯A	H⋯A	D⋯A	D—H⋯A	Motif	Direction
(1)
C13—H13⋯O11^i	2.47	3.403 (5)	167	R2^2(10)	–
C26—H26⋯O12^ii	2.55	3.272 (4)	132	R2^2(22)	–
N1—H1⋯I22	2.77	3.238 (2)	114	S(5)	–
C13—H13⋯O11	2.46	2.731 (4)	96	S(5)	–
C15—H15⋯O12	2.46	2.729 (5)	96	S(5)	–
(2)
N1—H1⋯O11^iii	2.53	3.195 (4)	133	C(9)	[010]
C17—H172⋯O11^iv	2.43	3.357 (5)	156	C(8)	[001]
C13—H13⋯O11	2.44	2.718 (5)	97	S(5)	-
C15—H15⋯O12	2.43	2.721 (5)	98	S(5)	–
(6)
C16—H16⋯O11^v	2.48	3.416 (5)	170	C(7)	[010]
N1—H1⋯Cg2^vi†	2.87	3.563 (4)	137	–	[001]
C12—H12⋯O11	2.40	2.704 (5)	98	S(5)	–
C14—H14⋯O12	2.45	2.737 (5)	97	S(5)	–
(7)
N3—H3⋯O12	2.34	3.107 (4)	146	D	–
C33—H33⋯O11^vii	2.53	3.147 (5)	123	R4^4(20)	–
N1—H1⋯I22	2.73	3.234 (3)	118	S(5)	–
C13—H13⋯O12	2.36	2.672 (5)	99	S(5)	–
C17—H171⋯O11	2.43	2.688 (5)	94	S(6)	–
C17—H172⋯O11	2.47	2.688 (5)	92	S(6)	–
N3—H3⋯I42	2.75	3.231 (3)	116	S(5)	–
C33—H33⋯O32	2.51	2.758 (4)	95	S(5)	–
C37—H371⋯O31	2.52	2.753 (4)	93	S(6)	–
C37—H372⋯O31	2.49	2.753 (4)	95	S(6)	–
Symmetry codes: (i) -x, 1 - y, 1 - z; (ii) -x, 2 - y, 1 - z; (iii) ; (iv) ; (v) x, -1 + y, z; (vi) ; (vii) 1 - x, -y, 1 - z.

†Cg2 is the centroid of the ring C21–C26.

Table 4
Parameters for iodo⋯nitro interactions (Å, °)

C—I⋯O—N	I⋯O	C—I⋯O	I⋯O—N	Motif^a	Direction
(2)
C23—I23⋯O12^i—N14^i	3.249 (3)	163.2 (2)	161.6 (2)	C(12)	[001]
(4)†
C2—I2⋯O131^i—N13^i	3.517 (2)	158.12 (7)	101.4 (2)	C(10)	[001]
(7)
C42—I42⋯O32^ii—N32^ii	3.523 (3)	103.3 (2)	117.1 (2)	C(9)	[10]
Reference: (a) Starbuck et al. (1999). Symmetry codes: (i) x, y, -1 + z; (ii) -1 + x, 1 + y, z.

†Original atom-labelling (Glidewell, Low et al., 2002).

Figure 1 A molecule of (1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2 Part of the crystal structure of (1) showing the formation of a chain of R2^2(10) and R2^2(22) rings along [010]. The atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (-x, 1 - y, 1 - z), (-x, 2 - y, 1 - z) and (x, -1 + y, z), respectively.

Figure 3 A molecule of (2), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4 Part of the crystal structure of (2) showing the formation of a C(9) chain along [010]. For the sake of clarity, H atoms bonded to C atoms are omitted. The atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (), (x, 1 + y, z) and (), respectively.

Figure 5 Part of the crystal structure of (2) showing the formation of a [001] chain built from C—H⋯O hydrogen bonds and iodo⋯nitro interactions. The atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (), (x, y, -1 + z), () and (x, y, 1 + z), respectively.

Figure 6 Stereoview of part of the crystal structure of (2) showing the formation of a [100] chain built from N—H⋯O and C—H⋯O hydrogen bonds.

Figure 7 Stereoview of part of the crystal structure of (2) showing the aromatic π⋯π stacking along [100]. For the sake of clarity, H atoms bonded to C atoms are omitted.

Figure 8 A molecule of (6), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 9 Part of the crystal structure of (6) showing the formation of a C(7) chain along [010]. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 + y, z) and (x, -1 + y, z), respectively.

Figure 10 Stereoview of part of the crystal structure of (6) showing the formation of a chain along [001] by means of N—H⋯π(arene) hydrogen bonds and π⋯π stacking interactions.

Figure 11 The two independent molecules of (7), showing the atom-labelling scheme: (a) molecule 1 and (b) molecule 2. Displacement ellipsoids are drawn at the 30% probability level.

Figure 12 Part of the crystal structure of (7) showing the formation of a four-molecule aggregate containing an R4^4(20) ring. For the sake of clarity the unit-cell box has been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 - x, -y, 1 - z).

Figure 13 Stereoview of part of the crystal structure of (7) showing the iodo⋯nitro and π⋯π stacking interactions which link the R4^4(20) aggregates into a ladder along [10]. For the sake of clarity, H atoms bonded to C atoms are omitted.

3. Results and discussion

3.1. Molecular conformations

The molecular conformations of iodo-(N-benzyl)anilines can be defined in terms of just four torsional angles and these are given in Table 2 for (1), (2) and (4)–(7). For the central spacer unit, the torsional angle C11—C17—N1—C21 shows that for (2) this unit is essentially trans planar, whereas for all other examples discussed here this torsional angle is close to ±90°, indicative of a markedly non-planar unit. The iodinated ring C21–C26 is generally nearly co-planar with the fragment C21—N1—C17. Since the labelling of the iodinated ring is determined by the location of the I substituent, the values show, for example, that in (1) and (2) the I substituent lies off different edges of the molecule: thus in (1) the I is on the same edge as the N—H bond, while in (2) it is on the opposite edge (Figs. 1 and 3). It seems possible that the short intramolecular N—H⋯I contacts in (1) (Table 3) play a significant role in controlling the overall conformation of (I). Likewise in the 2-iodo derivative (7), there is a short intramolecular N—H⋯I contact which may be significant in controlling the orientation of the iodinated ring. A similar difference occurs between (4) and (5) (Glidewell, Low et al., 2002). In (2) and (7), as well as in (4), the nitrated ring is nearly co-planar with the adjacent C11—C17—N1 fragment, but this is far from the case in (1), (5) and (6). In all cases there are some fairly short intramolecular C—H⋯O contacts (Table 3). The biggest deviation of the nitro group from co-planarity with the adjacent aryl ring occurs in (7), where moreover the two molecules show a marked difference: apart from this, the molecules in the selected asymmetric unit are close to being mirror images (see Fig. 11). It will be noted (see §3.2) that the structures of all these compounds exhibit direction-specific intermolecular interactions and it is thus probable that the energies associated with these intermolecular interactions are of similar magnitudes to the potential-energy barriers associated with rotation about the single bonds specified in Table 2.

One consequence of the conformational behaviour revealed by the torsional angles is that each molecule is chiral in the solid state, having no internal symmetry whatsoever. Compounds (1), (6) and (7) all crystallize in centrosymmetric space groups containing equal numbers of the two enantiomeric forms, as do (4) and (5) [P2₁/n and Pbca, respectively (Glidewell, Low et al., 2002)]: however, (2) crystallizes in the chiral space group P2₁2₁2₁ where each crystal can contain only one enantiomer. Since (2) is almost certainly racemic in solution, its crystallization is as a conglomerate: while the absolute configuration of the molecules in the crystal selected for study was readily determined, this configuration has no chemical significance.

The bond lengths and inter-bond angles show no unusual values.

3.2. Supramolecular structures

3.2.1. Compound (1)

In (1) (Fig. 1) there are neither N—H⋯O or X—H⋯π(arene) hydrogen bonds (where X = C or N) nor iodo⋯nitro or aromatic π⋯π stacking interactions. The only direction-specific interactions between the molecules are two independent C—H⋯O hydrogen bonds (Table 2), which combine to link the molecules into chains.

Atom C13 in the nitrated ring of the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro O11 in the molecule at (-x, 1 - y, 1 - z), so generating by inversion an R₂²(10) ring centred at (0, ½, ½): atom C26 in the iodinated ring at (x, y, z) similarly acts as a hydrogen-bond donor to O12 at (-x, 2 - y, 1 - z), producing an R₂²(22) ring centred at (0, 1, ½). The propagation by inversion of these two motifs thus generates a chain of rings running parallel to the [010] direction (Fig. 2).

3.2.2. Compound (2)

The supramolecular structure of (2) (Fig. 3), in contrast to that of (1), contains both N—H⋯O and C—H⋯O hydrogen bonds (Table 2) as well as both iodo⋯nitro interactions (Table 3) and aromatic π⋯π stacking interactions: as a result, this structure is three-dimensional, as opposed to the one-dimensional aggregation in (1). It is convenient to analyse the formation of the three-dimensional supramolecular network in (2) in terms of chains running parallel to the [100], [010] and [001] directions. There is an N—H⋯O hydrogen bond, albeit rather weak, which generates a C(9) chain running parallel to the [010] direction: N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to O11 in the molecule at (), thereby producing a chain generated by the 2₁ screw axis along (½, y, ¾) (Fig. 4).

The [001] chain formation involves both the iodo⋯nitro interaction and the C—H⋯O hydrogen bond. The C17 atom at (x, y, z) acts as a hydrogen-bond donor, via H172, to O11 at (), so producing a C(8) chain generated by the 2₁ screw axis along (¼, 0, z). At the same time, there is a fairly short two-centre iodo⋯nitro interaction between I23 in the molecule at (x, y, z) and O12 in that at (x, y, -1 + z), which generates by translation a C(12) chain along [001]. The combination of the two [001] motifs generates a chain of edge-fused R₃³(18) rings (Fig. 5).

These two chain types, parallel to [010] and [001], combine to form sheets parallel to (100) and these are linked by a combination of the two types of hydrogen bond. Atom N1 in the molecule at (), which lies in the (100) sheet in the domain 0.07 < x < 0.93, acts as a hydrogen-bond donor to O11 in the molecule at (), which forms part of the (100) sheet in the domain 1.07 < x < 1.93, and the resulting [100] chain (Fig. 6) links all of the (100) sheets into a three-dimensional framework. This linking of the (100) sheets is reinforced by π⋯π stacking interactions. The nitrated ring in the molecule at (x, y, z) makes an angle of only 4.1° with the iodinated rings of the two molecules at () and (): the interplanar spacings are both ca 3.45 Å with ring-centroid separations of 3.674 (5) and 3.760 (5) Å, respectively (Fig. 7).

3.2.3. Compound (6)

The supramolecular aggregation in (6) (Fig. 8) exhibits neither N—H⋯O hydrogen bonds nor iodo⋯nitro interactions: instead, the C—H⋯O hydrogen bond and the aromatic π⋯π stacking interaction are augmented by an N—H⋯π(arene) hydrogen bond, which forms in preference to the N—H⋯O hydrogen bond which might have been expected here. A single C—H⋯O hydrogen bond which involves a nitro O atom as an acceptor generates a simple chain running parallel to the [010] direction. Atom C16 in the nitrated ring of the molecule at (x, y, z) acts as a hydrogen-bond donor to O11 in the molecule at (x, 1 + y, z), so generating by translation a C(7) chain along [010] (Fig. 9).

The N—H⋯π(arene) hydrogen bond combines with the π⋯π stacking interactions to generate chains running parallel to the [001] direction. Amino atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the iodinated ring C21–C26, centroid Cg2 (Table 2), of the molecule at (). At the same time, the nitrated ring of the molecule at (x, y, z) forms π⋯π stacking interactions with the corresponding rings of the molecules at () and (): the angle between the adjacent rings is only ca 1.6°, and the centroid separation and the interplanar spacing are 3.844 (5) and ca 3.45 Å, respectively, corresponding to a centroid offset of ca 1.74 Å. Propagation of the mutually cooperative and mutually reinforcing N—H⋯π and π⋯π interactions thus produces a chain along [001] generated by the c-glide plane at y = 0.75 (Fig. 10). The combination of [010] and [001] chains generates a sheet parallel to (100), but there are no direction-specific interactions between adjacent sheets.

3.2.4. Compound (7)

Compound (7) (Fig. 11) crystallizes with Z′ = 2 in space group : within the selected asymmetric unit, N3 in molecule 2 (containing N3 and I42) acts as a hydrogen-bond donor to O12 in molecule 1 (containing N1 and I22), but N1 does not participate in any intermolecular hydrogen bonding. This difference in behaviour between N1 and N3 suffices to preclude any possibility of additional symmetry. In addition to the single N—H⋯O hydrogen bond within the asymmetric unit, the molecules are further linked into molecular ladders by a single, rather weak C—H⋯O hydrogen bond and a single, rather weak iodo⋯nitro interaction, whose action is reinforced by two independent aromatic π⋯π stacking interactions.

Atom C33 in the nitrated ring of molecule 2 at (x, y, z) acts as a hydrogen-bond donor to O11 in molecule 1 at (1 - x, -y, 1 - z): in combination with the N—H⋯O hydrogen bond within the asymmetric unit, this C—H⋯O hydrogen bond generates a centrosymmetric cyclic four-molecule aggregate, centred at (½, 0, ½) and characterized by an R₄⁴(20) ring (Fig. 12). The formation of this aggregate is reinforced by one of the π⋯π interactions. The nitrated rings C31–C36 of the type 2 molecules at (x, y, z) and (1 - x, -y, 1 - z) are parallel with an interplanar spacing of 3.385 (9) Å; the centroid separation is 3.685 (4) Å, corresponding to a near-ideal centroid offset of 1.46 (9) Å (Fig. 12).

These four-molecule aggregates are further linked by a combination of iodo⋯nitro and aromatic π⋯π stacking interactions to form the molecular ladder. Atom I42 in the type 2 molecule at (x, y, z) forms part of the cyclic aggregate centred at (½, 0, ½): this I atom forms a weak two-centre iodo⋯nitro interaction with O32 in the type 2 molecule at (-1 + x, 1 + y, z), which lies in the cyclic aggregate centred at (−½, 1, ½). At the same time, the nitrated ring C11–C16 of molecule 1 at (x, y, z) forms a π⋯π stacking interaction with the iodinated ring C41–C46 of molecule 2 at (-x, 1 - y, 1 - z), which is also a part of the cyclic aggregate centred at (−½, 1, ½) (Fig. 13). In this manner the molecules are linked by the cooperative combination of four types of intermolecular interactions into ladders running parallel to the [10] direction.

3.3. General comments on the supramolecular structures

The molecular constitutions of (1)–(9) [see (II)] allow the possibility of six different types of direction-specific intermolecular interaction. These are N—H⋯O and C—H⋯O, hydrogen bonds, iodo⋯nitro interactions, and aromatic π⋯π stacking interactions. In the event, no single compound in this series whose structure has been determined to date exhibits more than four of these types, while (1) exhibits only one type, namely C—H⋯O hydrogen bonds. Compounds (4)–(6) all exhibit three types of direction-specific intermolecular interaction, but the selection is, in fact, different for each: while the structures of all three of these compounds contain C—H⋯O hydrogen bonds, only that of (5) contains N—H⋯O and C—H⋯π(arene) hydrogen bonds, only that of (6) contains N—H⋯π(arene) hydrogen bonds, and only that of (4) contains iodo⋯nitro interactions. In addition, while the structures of both (4) and (6) contain aromatic π⋯π stacking interactions, these are absent from the structure of (5).

Not only do the number and identity of the types of intermolecular interactions vary, but the structural consequences of these interactions also show a wide range of behaviour. Thus, while (2) and (7) both contain the same four types of intermolecular interactions, namely N—H⋯O and C—H⋯O hydrogen bonds, and iodo⋯nitro and π⋯π stacking interactions, the consequences of these are entirely different in that the overall supramolecular structures of (2) and (7) are three- and one-dimensional, respectively. Compounds (1) and (7), exhibiting one and four types, respectively, in the intermolecular interactions, both have one-dimensional supra­molecular structures; (5) and (6) both have two-dimensional supramolecular structures; (2) and (4), exhibiting four and three types, respectively, of intermolecular interaction, both have three-dimensional supramolecular structures.

4. Concluding comments

The molecular conformations of the isomeric iodo-N-(nitrobenzyl)anilines (see §3.1) and the patterns in their supramolecular aggregation (see §3.3) point to a subtle interplay of the weak direction-specific intermolecular forces. Weak forces of the types manifest here, dependent upon molecular polarizability and polarization, are not easy to model computationally. The variations in the supramolecular aggregation behaviour within an extended series of isomeric compounds, such as those described here, provide a keen test of computational methods for crystal-structure prediction (Lommerse et al., 2000; Motherwell et al., 2002): the accurate prediction of behaviour across such a series of isomeric species would generate real confidence in the efficacy of the predictive methods employed.

Supporting information

S1. Comment

In full text version

S2. Experimental

In full text version

S3. Refinement

In full text version

Computing details

For all compounds, data collection: Kappa-CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b) for (1), (2), (7); OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (6). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a) for (1), (2), (7); OSCAIL and SHELXS97 (Sheldrick, 1997) for (6). For all compounds, molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

In full text version

(1) 2-Iodo-N-(4-nitrobenzyl)aniline

Crystal data

C13H11IN2O2	F(000) = 688
Mr = 354.14	Dx = 1.878 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2850 reflections
a = 16.1564 (6) Å	θ = 3.3–27.5°
b = 9.3589 (3) Å	µ = 2.55 mm^−1
c = 8.3326 (3) Å	T = 120 K
β = 96.333 (1)°	Block, red
V = 1252.25 (8) Å^3	0.32 × 0.22 × 0.15 mm
Z = 4

Data collection

Kappa-CCD diffractometer	2850 independent reflections
Radiation source: frotating anode	2641 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −20→20
Tmin = 0.496, Tmax = 0.682	k = −11→12
8013 measured reflections	l = −7→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0212P)^2 + 2.0006P] where P = (Fo^2 + 2Fc^2)/3
2850 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 1.10 e Å^−3
0 restraints	Δρmin = −0.74 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.34831 (15)	0.8976 (3)	0.5028 (3)	0.0208 (5)
C11	0.21295 (17)	0.8913 (3)	0.6217 (3)	0.0192 (5)
C12	0.19261 (19)	0.7557 (3)	0.5640 (4)	0.0281 (6)
C13	0.1112 (2)	0.7071 (4)	0.5551 (5)	0.0318 (7)
C14	0.0509 (2)	0.7958 (3)	0.6038 (4)	0.0245 (6)
N14	−0.03558 (17)	0.7472 (3)	0.5918 (3)	0.0297 (6)
O11	−0.05405 (19)	0.6383 (4)	0.5214 (5)	0.0834 (13)
O12	−0.0862 (2)	0.8140 (4)	0.6529 (6)	0.0817 (14)
C15	0.0693 (2)	0.9301 (4)	0.6644 (5)	0.0389 (8)
C16	0.1511 (2)	0.9776 (4)	0.6731 (5)	0.0369 (8)
C17	0.30204 (17)	0.9441 (3)	0.6341 (3)	0.0221 (6)
C21	0.33837 (17)	0.9641 (3)	0.3538 (3)	0.0175 (5)
C22	0.39526 (16)	0.9418 (3)	0.2390 (3)	0.0169 (5)
I22	0.499804 (10)	0.810111 (19)	0.29835 (2)	0.01968 (8)
C23	0.38454 (17)	1.0054 (3)	0.0883 (3)	0.0201 (5)
C24	0.31735 (19)	1.0959 (3)	0.0458 (3)	0.0223 (6)
C25	0.26030 (18)	1.1191 (3)	0.1566 (4)	0.0233 (6)
C26	0.27045 (18)	1.0544 (3)	0.3076 (3)	0.0215 (6)
H1	0.3833	0.8256	0.5187	0.08 (2)*
H12	0.2348	0.6955	0.5302	0.034 (11)*
H13	0.0972	0.6138	0.5159	0.064 (14)*
H15	0.0270	0.9891	0.6996	0.056 (13)*
H16	0.1649	1.0701	0.7146	0.051 (12)*
H171	0.3017	1.0499	0.6368	0.025 (9)*
H172	0.3317	0.9105	0.7375	0.022 (8)*
H23	0.4234	0.9872	0.0131	0.042 (11)*
H24	0.3106	1.1411	−0.0569	0.023 (8)*
H25	0.2139	1.1799	0.1286	0.023 (9)*
H26	0.2306	1.0716	0.3811	0.032 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0214 (12)	0.0234 (12)	0.0190 (11)	0.0033 (9)	0.0087 (9)	0.0018 (9)
C11	0.0212 (13)	0.0211 (14)	0.0167 (12)	−0.0015 (10)	0.0078 (10)	0.0007 (10)
C12	0.0241 (15)	0.0264 (16)	0.0340 (17)	0.0023 (12)	0.0044 (12)	−0.0099 (13)
C13	0.0242 (16)	0.0283 (17)	0.0430 (19)	−0.0015 (12)	0.0041 (14)	−0.0113 (14)
C14	0.0224 (15)	0.0295 (16)	0.0225 (14)	−0.0011 (11)	0.0061 (12)	0.0055 (11)
N14	0.0252 (13)	0.0325 (15)	0.0321 (14)	−0.0023 (11)	0.0068 (11)	0.0080 (12)
O11	0.0298 (16)	0.095 (3)	0.127 (3)	−0.0225 (17)	0.0141 (18)	−0.067 (3)
O12	0.0360 (18)	0.065 (2)	0.154 (4)	−0.0124 (14)	0.054 (2)	−0.037 (2)
C15	0.0291 (17)	0.0275 (17)	0.066 (2)	−0.0020 (13)	0.0302 (16)	−0.0096 (17)
C16	0.0343 (18)	0.0243 (16)	0.057 (2)	−0.0061 (13)	0.0264 (16)	−0.0138 (15)
C17	0.0220 (14)	0.0272 (15)	0.0187 (13)	−0.0028 (11)	0.0094 (10)	−0.0035 (12)
C21	0.0198 (12)	0.0140 (12)	0.0197 (12)	−0.0017 (10)	0.0065 (10)	−0.0030 (10)
C22	0.0170 (12)	0.0135 (12)	0.0208 (13)	−0.0008 (10)	0.0047 (9)	−0.0029 (10)
I22	0.01576 (11)	0.02505 (12)	0.01885 (11)	0.00215 (6)	0.00468 (7)	0.00052 (7)
C23	0.0207 (13)	0.0200 (13)	0.0203 (13)	−0.0030 (10)	0.0055 (10)	−0.0018 (11)
C24	0.0274 (15)	0.0191 (14)	0.0205 (13)	−0.0008 (11)	0.0033 (11)	0.0026 (11)
C25	0.0237 (14)	0.0177 (14)	0.0285 (15)	0.0024 (11)	0.0028 (12)	0.0002 (11)
C26	0.0227 (13)	0.0180 (13)	0.0250 (14)	0.0003 (11)	0.0088 (11)	−0.0021 (11)

Geometric parameters (Å, º)

N1—C21	1.382 (4)	C15—H15	0.95
N1—C17	1.458 (3)	C16—H16	0.95
N1—H1	0.88	C17—H171	0.99
C11—C12	1.383 (4)	C17—H172	0.99
C11—C16	1.388 (4)	C21—C26	1.405 (4)
C11—C17	1.515 (4)	C21—C22	1.413 (4)
C12—C13	1.386 (4)	C22—C23	1.383 (4)
C12—H12	0.95	C22—I22	2.105 (3)
C13—C14	1.375 (4)	C23—C24	1.392 (4)
C13—H13	0.95	C23—H23	0.95
C14—C15	1.374 (4)	C24—C25	1.392 (4)
C14—N14	1.463 (4)	C24—H24	0.95
N14—O12	1.188 (4)	C25—C26	1.390 (4)
N14—O11	1.197 (4)	C25—H25	0.95
C15—C16	1.389 (5)	C26—H26	0.95
C21—N1—C17	121.4 (2)	N1—C17—C11	114.4 (2)
C21—N1—H1	119.3	N1—C17—H171	108.7
C17—N1—H1	119.3	C11—C17—H171	108.7
C12—C11—C16	119.3 (3)	N1—C17—H172	108.6
C12—C11—C17	120.7 (3)	C11—C17—H172	108.7
C16—C11—C17	120.0 (3)	H171—C17—H172	107.6
C11—C12—C13	120.5 (3)	N1—C21—C26	121.8 (2)
C11—C12—H12	119.8	N1—C21—C22	121.4 (2)
C13—C12—H12	119.8	C26—C21—C22	116.7 (2)
C14—C13—C12	119.0 (3)	C23—C22—C21	121.7 (2)
C14—C13—H13	120.5	C23—C22—I22	118.84 (19)
C12—C13—H13	120.5	C21—C22—I22	119.50 (19)
C15—C14—C13	122.0 (3)	C22—C23—C24	120.6 (3)
C15—C14—N14	118.4 (3)	C22—C23—H23	119.7
C13—C14—N14	119.6 (3)	C24—C23—H23	119.7
O12—N14—O11	120.8 (3)	C23—C24—C25	118.8 (3)
O12—N14—C14	120.3 (3)	C23—C24—H24	120.6
O11—N14—C14	118.9 (3)	C25—C24—H24	120.6
C14—C15—C16	118.5 (3)	C26—C25—C24	120.8 (3)
C14—C15—H15	120.8	C26—C25—H25	119.6
C16—C15—H15	120.8	C24—C25—H25	119.6
C11—C16—C15	120.7 (3)	C25—C26—C21	121.4 (3)
C11—C16—H16	119.6	C25—C26—H26	119.3
C15—C16—H16	119.6	C21—C26—H26	119.3
C16—C11—C12—C13	1.0 (5)	C12—C11—C17—N1	37.1 (4)
C17—C11—C12—C13	179.1 (3)	C16—C11—C17—N1	−144.8 (3)
C11—C12—C13—C14	0.3 (5)	C17—N1—C21—C26	−15.7 (4)
C12—C13—C14—C15	−1.5 (5)	C17—N1—C21—C22	165.7 (2)
C12—C13—C14—N14	178.7 (3)	N1—C21—C22—C23	178.5 (3)
C15—C14—N14—O12	−10.0 (5)	C26—C21—C22—C23	−0.1 (4)
C13—C14—N14—O12	169.8 (4)	N1—C21—C22—I22	−2.2 (3)
C15—C14—N14—O11	171.0 (4)	C26—C21—C22—I22	179.25 (19)
C13—C14—N14—O11	−9.2 (5)	C21—C22—C23—C24	0.9 (4)
C13—C14—C15—C16	1.3 (6)	I22—C22—C23—C24	−178.4 (2)
N14—C14—C15—C16	−178.8 (3)	C22—C23—C24—C25	−1.2 (4)
C12—C11—C16—C15	−1.1 (5)	C23—C24—C25—C26	0.6 (4)
C17—C11—C16—C15	−179.2 (3)	C24—C25—C26—C21	0.2 (4)
C14—C15—C16—C11	0.0 (6)	N1—C21—C26—C25	−179.0 (3)
C21—N1—C17—C11	79.3 (3)	C22—C21—C26—C25	−0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O11^i	0.95	2.47	3.403 (5)	167
C26—H26···O12^ii	0.95	2.55	3.272 (4)	132

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

(2) 3-Iodo-N-(4-nitrobenzyl))aniline

Crystal data

C13H11IN2O2	F(000) = 688
Mr = 354.14	Dx = 1.903 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2783 reflections
a = 7.0966 (2) Å	θ = 2.9–27.5°
b = 12.5908 (4) Å	µ = 2.59 mm^−1
c = 13.8360 (6) Å	T = 120 K
V = 1236.27 (8) Å^3	Needle, orange
Z = 4	0.38 × 0.05 × 0.03 mm

Data collection

Kappa-CCD diffractometer	2783 independent reflections
Radiation source: rotating anode	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −8→9
Tmin = 0.440, Tmax = 0.927	k = −16→16
9541 measured reflections	l = −15→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.050	w = 1/[σ^2(Fo^2) + (0.0137P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2783 reflections	Δρmax = 0.54 e Å^−3
163 parameters	Δρmin = −0.61 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1191 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.3919 (5)	0.3395 (3)	0.4693 (2)	0.0218 (8)
C17	0.4045 (5)	0.2280 (3)	0.4779 (3)	0.0207 (9)
C11	0.3936 (4)	0.1839 (2)	0.5785 (3)	0.0168 (7)
C12	0.4180 (4)	0.0752 (3)	0.5892 (3)	0.0206 (8)
C13	0.4024 (5)	0.0272 (3)	0.6789 (3)	0.0204 (9)
C14	0.3602 (4)	0.0912 (3)	0.7580 (3)	0.0164 (8)
N14	0.3393 (4)	0.0413 (3)	0.8530 (2)	0.0236 (8)
O11	0.3704 (4)	−0.0537 (2)	0.86032 (19)	0.0325 (7)
O12	0.2921 (4)	0.09823 (19)	0.92151 (19)	0.0302 (6)
C15	0.3389 (4)	0.1994 (3)	0.7494 (3)	0.0181 (8)
C16	0.3554 (5)	0.2455 (3)	0.6593 (2)	0.0176 (9)
C21	0.3891 (5)	0.3868 (3)	0.3778 (3)	0.0177 (8)
C22	0.3470 (5)	0.3278 (3)	0.2944 (3)	0.0183 (8)
C23	0.3437 (5)	0.3795 (3)	0.2056 (2)	0.0182 (8)
I23	0.28995 (3)	0.28735 (2)	0.081314 (17)	0.02517 (8)
C24	0.3805 (5)	0.4864 (3)	0.1961 (3)	0.0196 (8)
C25	0.4207 (5)	0.5439 (3)	0.2803 (3)	0.0217 (9)
C26	0.4255 (5)	0.4944 (3)	0.3688 (3)	0.0188 (8)
H1	0.3858	0.3793	0.5214	0.026*
H171	0.5253	0.2049	0.4489	0.025*
H172	0.3019	0.1960	0.4392	0.025*
H12	0.4458	0.0330	0.5341	0.025*
H13	0.4201	−0.0472	0.6863	0.024*
H15	0.3132	0.2417	0.8047	0.022*
H17	0.3405	0.3201	0.6526	0.021*
H22	0.3212	0.2539	0.2986	0.022*
H24	0.3786	0.5200	0.1346	0.024*
H25	0.4451	0.6179	0.2761	0.026*
H26	0.4542	0.5348	0.4249	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0356 (19)	0.021 (2)	0.0086 (16)	0.0022 (16)	0.0016 (14)	−0.0001 (14)
C17	0.0159 (19)	0.027 (3)	0.019 (2)	0.0013 (18)	−0.0020 (15)	0.0058 (19)
C11	0.0110 (17)	0.022 (2)	0.0170 (18)	−0.0032 (12)	−0.0049 (16)	0.0027 (18)
C12	0.021 (2)	0.022 (2)	0.019 (2)	0.0022 (14)	0.0004 (18)	−0.0040 (19)
C13	0.016 (2)	0.021 (2)	0.024 (2)	−0.0020 (15)	−0.0018 (15)	0.0027 (17)
C14	0.0115 (17)	0.026 (2)	0.0120 (19)	−0.0078 (14)	−0.0025 (15)	0.0044 (16)
N14	0.021 (2)	0.032 (2)	0.0178 (18)	−0.0032 (14)	−0.0028 (13)	0.0064 (16)
O11	0.0441 (18)	0.0251 (18)	0.0282 (16)	0.0076 (13)	0.0026 (13)	0.0123 (13)
O12	0.0436 (15)	0.0319 (15)	0.0149 (13)	−0.0030 (12)	0.0024 (17)	0.0032 (13)
C15	0.0173 (18)	0.023 (2)	0.0136 (17)	0.0000 (15)	−0.0001 (13)	−0.0005 (18)
C16	0.0169 (19)	0.016 (2)	0.020 (2)	−0.0009 (13)	−0.0003 (15)	0.0030 (15)
C21	0.0127 (19)	0.025 (2)	0.0149 (19)	0.0034 (16)	0.0007 (14)	0.0002 (16)
C22	0.019 (2)	0.018 (2)	0.018 (2)	0.0028 (14)	0.0009 (14)	−0.0014 (15)
C23	0.016 (2)	0.023 (2)	0.015 (2)	0.0015 (15)	−0.0023 (14)	−0.0029 (16)
I23	0.03187 (13)	0.02975 (13)	0.01389 (12)	0.00336 (12)	−0.00212 (10)	−0.00242 (13)
C24	0.0205 (19)	0.024 (2)	0.0148 (19)	0.0040 (16)	0.0036 (16)	0.0076 (17)
C25	0.019 (2)	0.018 (2)	0.028 (2)	0.0029 (15)	−0.0036 (15)	0.0041 (17)
C26	0.018 (2)	0.021 (2)	0.0182 (19)	0.0008 (16)	−0.0020 (15)	−0.0003 (17)

Geometric parameters (Å, º)

N1—C21	1.399 (4)	N14—O12	1.235 (4)
N1—C17	1.412 (4)	C15—C16	1.380 (5)
N1—H1	0.88	C15—H15	0.95
C17—C11	1.501 (5)	C16—H17	0.95
C17—H171	0.99	C21—C26	1.384 (5)
C17—H172	0.99	C21—C22	1.404 (5)
C11—C12	1.387 (4)	C22—C23	1.391 (5)
C11—C16	1.388 (5)	C22—H22	0.95
C12—C13	1.385 (5)	C23—C24	1.378 (5)
C12—H12	0.95	C23—I23	2.109 (3)
C13—C14	1.391 (5)	C24—C25	1.400 (5)
C13—H13	0.95	C24—H24	0.95
C14—C15	1.375 (5)	C25—C26	1.375 (5)
C14—N14	1.464 (4)	C25—H25	0.95
N14—O11	1.220 (4)	C26—H26	0.95
C21—N1—C17	120.1 (3)	C14—C15—C16	119.1 (3)
C21—N1—H1	120.0	C14—C15—H15	120.5
C17—N1—H1	120.0	C16—C15—H15	120.5
N1—C17—C11	116.3 (3)	C15—C16—C11	120.6 (3)
N1—C17—H171	108.2	C15—C16—H17	119.7
C11—C17—H171	108.2	C11—C16—H17	119.7
N1—C17—H172	108.2	C26—C21—N1	119.6 (3)
C11—C17—H172	108.2	C26—C21—C22	119.0 (3)
H171—C17—H172	107.4	N1—C21—C22	121.4 (3)
C12—C11—C16	119.3 (4)	C23—C22—C21	118.8 (3)
C12—C11—C17	117.3 (4)	C23—C22—H22	120.6
C16—C11—C17	123.4 (3)	C21—C22—H22	120.6
C13—C12—C11	121.1 (4)	C24—C23—C22	122.6 (3)
C13—C12—H12	119.5	C24—C23—I23	119.6 (3)
C11—C12—H12	119.5	C22—C23—I23	117.8 (3)
C12—C13—C14	118.0 (4)	C23—C24—C25	117.7 (3)
C12—C13—H13	121.0	C23—C24—H24	121.2
C14—C13—H13	121.0	C25—C24—H24	121.2
C15—C14—C13	121.9 (3)	C26—C25—C24	120.8 (4)
C15—C14—N14	119.4 (3)	C26—C25—H25	119.6
C13—C14—N14	118.6 (3)	C24—C25—H25	119.6
O11—N14—O12	123.6 (3)	C25—C26—C21	121.2 (4)
O11—N14—C14	118.5 (3)	C25—C26—H26	119.4
O12—N14—C14	117.9 (3)	C21—C26—H26	119.4
C21—N1—C17—C11	−176.0 (3)	C12—C11—C16—C15	−1.0 (4)
N1—C17—C11—C12	−175.9 (3)	C17—C11—C16—C15	177.1 (3)
N1—C17—C11—C16	6.0 (5)	C17—N1—C21—C26	−163.4 (3)
C16—C11—C12—C13	0.9 (5)	C17—N1—C21—C22	17.7 (6)
C17—C11—C12—C13	−177.3 (3)	C26—C21—C22—C23	0.2 (5)
C11—C12—C13—C14	0.4 (5)	N1—C21—C22—C23	179.1 (3)
C12—C13—C14—C15	−1.7 (5)	C21—C22—C23—C24	0.1 (5)
C12—C13—C14—N14	178.7 (3)	C21—C22—C23—I23	177.8 (2)
C15—C14—N14—O11	−175.4 (3)	C22—C23—C24—C25	−0.6 (5)
C13—C14—N14—O11	4.2 (5)	I23—C23—C24—C25	−178.2 (2)
C15—C14—N14—O12	4.1 (4)	C23—C24—C25—C26	0.8 (5)
C13—C14—N14—O12	−176.2 (3)	C24—C25—C26—C21	−0.6 (5)
C13—C14—C15—C16	1.6 (5)	N1—C21—C26—C25	−178.9 (3)
N14—C14—C15—C16	−178.8 (3)	C22—C21—C26—C25	0.1 (5)
C14—C15—C16—C11	−0.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O11^i	0.88	2.53	3.196 (4)	133
C17—H172···O11^ii	0.99	2.43	3.357 (5)	156

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

(6) 4-Iodo-N-(3-nitrobenzyl))aniline

Crystal data

C13H11IN2O2	F(000) = 688
Mr = 354.14	Dx = 1.862 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2785 reflections
a = 21.2778 (15) Å	θ = 3.1–27.5°
b = 8.1809 (5) Å	µ = 2.53 mm^−1
c = 7.2793 (4) Å	T = 120 K
β = 94.316 (2)°	Needle, yellow
V = 1263.53 (14) Å^3	0.48 × 0.04 × 0.02 mm
Z = 4

Data collection

Kappa-CCD diffractometer	2785 independent reflections
Radiation source: rotating anode	1934 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan SORTAV (Blessing, 1995 & 1997)	h = −27→27
Tmin = 0.377, Tmax = 0.951	k = −10→10
12705 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0209P)^2] where P = (Fo^2 + 2Fc^2)/3
2785 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 1.13 e Å^−3
0 restraints	Δρmin = −0.60 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.29471 (14)	0.6052 (4)	0.0718 (4)	0.0251 (8)
C11	0.17805 (17)	0.6034 (5)	0.0486 (4)	0.0174 (8)
C12	0.17247 (16)	0.7717 (5)	0.0569 (4)	0.0178 (8)
C13	0.11592 (18)	0.8393 (5)	0.1011 (5)	0.0179 (9)
N13	0.11125 (17)	1.0189 (4)	0.1087 (4)	0.0244 (8)
O11	0.15922 (13)	1.0989 (3)	0.0901 (4)	0.0360 (7)
O12	0.05994 (13)	1.0807 (3)	0.1341 (4)	0.0360 (7)
C14	0.06417 (18)	0.7463 (5)	0.1383 (4)	0.0227 (9)
C15	0.07033 (18)	0.5784 (5)	0.1321 (5)	0.0255 (9)
C16	0.12658 (19)	0.5077 (5)	0.0873 (5)	0.0246 (9)
C17	0.23833 (19)	0.5273 (5)	−0.0108 (5)	0.0266 (10)
C21	0.32330 (17)	0.5586 (4)	0.2411 (5)	0.0178 (8)
C22	0.29209 (17)	0.4628 (5)	0.3662 (5)	0.0201 (9)
C23	0.32217 (17)	0.4212 (5)	0.5346 (5)	0.0200 (8)
C24	0.38304 (17)	0.4743 (4)	0.5817 (4)	0.0190 (8)
I24	0.429933 (12)	0.40696 (3)	0.83507 (3)	0.02594 (10)
C25	0.41432 (17)	0.5698 (4)	0.4606 (5)	0.0185 (8)
C26	0.38440 (17)	0.6114 (4)	0.2919 (5)	0.0196 (9)
H1	0.3197	0.6537	−0.0023	0.030*
H12	0.2070	0.8399	0.0327	0.021*
H14	0.0258	0.7960	0.1671	0.027*
H15	0.0359	0.5107	0.1585	0.031*
H16	0.1300	0.3920	0.0831	0.029*
H17A	0.2391	0.4101	0.0231	0.032*
H17B	0.2384	0.5345	−0.1466	0.032*
H22	0.2502	0.4266	0.3349	0.024*
H23	0.3010	0.3558	0.6185	0.024*
H25	0.4560	0.6064	0.4932	0.022*
H26	0.4059	0.6772	0.2091	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0207 (18)	0.031 (2)	0.0245 (18)	0.0029 (16)	0.0050 (14)	0.0043 (15)
C11	0.020 (2)	0.018 (2)	0.0131 (18)	0.0020 (18)	−0.0044 (14)	−0.0005 (15)
C12	0.016 (2)	0.021 (2)	0.0156 (18)	−0.0060 (17)	−0.0028 (14)	−0.0003 (16)
C13	0.023 (2)	0.016 (2)	0.0146 (19)	0.0032 (18)	−0.0012 (15)	−0.0008 (15)
N13	0.027 (2)	0.022 (2)	0.0238 (18)	0.0045 (18)	0.0003 (14)	0.0009 (14)
O11	0.0300 (18)	0.0174 (17)	0.062 (2)	−0.0029 (15)	0.0091 (14)	0.0015 (14)
O12	0.0288 (18)	0.0281 (18)	0.0516 (19)	0.0147 (15)	0.0068 (13)	−0.0023 (14)
C14	0.020 (2)	0.030 (3)	0.018 (2)	0.0019 (19)	0.0020 (15)	0.0001 (17)
C15	0.025 (2)	0.030 (3)	0.022 (2)	−0.007 (2)	0.0024 (16)	0.0038 (17)
C16	0.036 (3)	0.012 (2)	0.024 (2)	0.000 (2)	−0.0043 (17)	−0.0021 (16)
C17	0.035 (3)	0.023 (2)	0.020 (2)	0.009 (2)	−0.0011 (17)	−0.0019 (17)
C21	0.020 (2)	0.018 (2)	0.0163 (19)	0.0089 (16)	0.0025 (15)	−0.0007 (15)
C22	0.017 (2)	0.020 (2)	0.023 (2)	0.0005 (17)	0.0021 (16)	−0.0037 (16)
C23	0.023 (2)	0.016 (2)	0.022 (2)	0.0040 (18)	0.0060 (15)	0.0008 (16)
C24	0.026 (2)	0.012 (2)	0.019 (2)	0.0034 (17)	0.0013 (16)	−0.0019 (15)
I24	0.02652 (16)	0.03048 (18)	0.02068 (15)	0.00257 (14)	0.00091 (10)	0.00406 (12)
C25	0.016 (2)	0.016 (2)	0.024 (2)	0.0023 (17)	0.0035 (15)	−0.0034 (16)
C26	0.022 (2)	0.017 (2)	0.021 (2)	0.0019 (18)	0.0086 (15)	0.0022 (16)

Geometric parameters (Å, º)

N1—C21	1.386 (4)	C14—H14	0.95
N1—C17	1.449 (5)	C15—C16	1.390 (5)
N1—H1	0.8799	C15—H15	0.95
C17—C11	1.518 (5)	C16—H16	0.95
C17—H17A	0.99	C21—C26	1.393 (5)
C17—H17B	0.99	C21—C22	1.406 (5)
C11—C12	1.384 (5)	C22—C23	1.382 (5)
C11—C16	1.392 (5)	C22—H22	0.95
C12—C13	1.384 (5)	C23—C24	1.385 (5)
C12—H12	0.95	C23—H23	0.95
C13—C14	1.382 (5)	C24—C25	1.385 (5)
C13—N13	1.474 (5)	C24—I24	2.104 (3)
N13—O11	1.229 (4)	C25—C26	1.383 (5)
N13—O12	1.230 (4)	C25—H25	0.95
C14—C15	1.381 (5)	C26—H26	0.95
C21—N1—C17	122.9 (3)	C14—C15—C16	120.5 (4)
C21—N1—H1	115.0	C14—C15—H15	119.8
C17—N1—H1	117.6	C16—C15—H15	119.8
N1—C17—C11	113.1 (3)	C15—C16—C11	121.2 (4)
N1—C17—H17A	109.0	C15—C16—H16	119.4
C11—C17—H17A	109.0	C11—C16—H16	119.4
N1—C17—H17B	109.0	N1—C21—C26	119.3 (3)
C11—C17—H17B	109.0	N1—C21—C22	122.1 (3)
H17A—C17—H17B	107.8	C26—C21—C22	118.5 (3)
C12—C11—C16	118.6 (3)	C23—C22—C21	120.1 (3)
C12—C11—C17	119.9 (3)	C23—C22—H22	119.9
C16—C11—C17	121.4 (3)	C21—C22—H22	119.9
C11—C12—C13	119.1 (3)	C22—C23—C24	120.3 (3)
C11—C12—H12	120.4	C22—C23—H23	119.9
C13—C12—H12	120.4	C24—C23—H23	119.9
C14—C13—C12	123.0 (3)	C23—C24—C25	120.3 (3)
C14—C13—N13	119.0 (3)	C23—C24—I24	120.5 (3)
C12—C13—N13	118.0 (3)	C25—C24—I24	119.1 (3)
O11—N13—O12	123.5 (3)	C26—C25—C24	119.5 (3)
O11—N13—C13	117.9 (3)	C26—C25—H25	120.2
O12—N13—C13	118.6 (3)	C24—C25—H25	120.2
C15—C14—C13	117.5 (4)	C25—C26—C21	121.2 (3)
C15—C14—H14	121.2	C25—C26—H26	119.4
C13—C14—H14	121.2	C21—C26—H26	119.4
C21—N1—C17—C11	87.8 (4)	C12—C11—C16—C15	0.6 (5)
N1—C17—C11—C12	43.3 (4)	C17—C11—C16—C15	−176.5 (3)
N1—C17—C11—C16	−139.7 (3)	C17—N1—C21—C26	165.2 (3)
C16—C11—C12—C13	−0.8 (5)	C17—N1—C21—C22	−16.5 (5)
C17—C11—C12—C13	176.3 (3)	N1—C21—C22—C23	−179.1 (3)
C11—C12—C13—C14	0.2 (5)	C26—C21—C22—C23	−0.7 (5)
C11—C12—C13—N13	−179.9 (3)	C21—C22—C23—C24	0.4 (5)
C14—C13—N13—O11	174.2 (3)	C22—C23—C24—C25	0.1 (5)
C12—C13—N13—O11	−5.8 (4)	C22—C23—C24—I24	−178.6 (3)
C14—C13—N13—O12	−5.4 (5)	C23—C24—C25—C26	−0.2 (5)
C12—C13—N13—O12	174.6 (3)	I24—C24—C25—C26	178.5 (3)
C12—C13—C14—C15	0.6 (5)	C24—C25—C26—C21	−0.2 (5)
N13—C13—C14—C15	−179.3 (3)	N1—C21—C26—C25	179.0 (3)
C13—C14—C15—C16	−0.8 (5)	C22—C21—C26—C25	0.6 (5)
C14—C15—C16—C11	0.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O11^i	0.95	2.48	3.416 (5)	170
N1—H1···Cg2^ii	0.88	2.87	3.563 (4)	137

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

(7) 2-Iodo-N-(2-nitrobenzyl))aniline

Crystal data

C13H11IN2O2	Z = 4
Mr = 354.14	F(000) = 688
Triclinic, P1	Dx = 1.841 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1685 (1) Å	Cell parameters from 5760 reflections
b = 10.8834 (2) Å	θ = 3.1–27.5°
c = 15.4372 (2) Å	µ = 2.50 mm^−1
α = 76.9219 (9)°	T = 120 K
β = 80.0727 (7)°	Block, orange
γ = 74.2167 (7)°	0.22 × 0.18 × 0.12 mm
V = 1277.36 (3) Å^3

Data collection

Kappa-CCD diffractometer	5760 independent reflections
Radiation source: rotating anode	5317 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −10→10
Tmin = 0.597, Tmax = 0.738	k = −14→13
5760 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 2.2937P] where P = (Fo^2 + 2Fc^2)/3
5760 reflections	(Δ/σ)max = 0.003
325 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −1.65 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.4705 (4)	0.2423 (3)	0.9345 (2)	0.0285 (6)
C17	0.4270 (4)	0.2768 (3)	0.8436 (2)	0.0243 (7)
C11	0.2877 (4)	0.4032 (3)	0.8265 (2)	0.0201 (6)
C12	0.2322 (4)	0.4634 (3)	0.7422 (2)	0.0210 (6)
N12	0.3066 (4)	0.4045 (3)	0.6618 (2)	0.0292 (7)
O11	0.3889 (5)	0.2939 (3)	0.6714 (2)	0.0500 (8)
O12	0.2783 (6)	0.4727 (3)	0.5893 (2)	0.0536 (9)
C13	0.1083 (5)	0.5799 (4)	0.7286 (3)	0.0295 (8)
C14	0.0350 (5)	0.6411 (4)	0.7996 (3)	0.0340 (9)
C15	0.0868 (5)	0.5853 (4)	0.8841 (3)	0.0326 (8)
C16	0.2114 (4)	0.4685 (4)	0.8962 (2)	0.0255 (7)
C21	0.3852 (4)	0.1721 (3)	1.0040 (2)	0.0225 (6)
C22	0.4396 (4)	0.1328 (3)	1.0891 (2)	0.0244 (7)
I22	0.65858 (3)	0.18196 (3)	1.112805 (16)	0.03433 (10)
C23	0.3554 (5)	0.0627 (4)	1.1602 (3)	0.0335 (8)
C24	0.2062 (5)	0.0271 (3)	1.1469 (3)	0.0350 (9)
C25	0.1520 (5)	0.0662 (4)	1.0658 (3)	0.0348 (9)
C26	0.2359 (4)	0.1373 (4)	0.9942 (3)	0.0293 (7)
N3	0.3333 (4)	0.4467 (3)	0.3894 (2)	0.0269 (6)
C37	0.4815 (4)	0.3380 (3)	0.3986 (2)	0.0241 (7)
C31	0.4493 (4)	0.2081 (3)	0.3948 (2)	0.0191 (6)
C32	0.5812 (4)	0.0980 (3)	0.3838 (2)	0.0182 (6)
N32	0.7619 (3)	0.1039 (3)	0.37277 (19)	0.0218 (6)
O31	0.8008 (3)	0.1726 (3)	0.41571 (18)	0.0297 (5)
O32	0.8636 (3)	0.0400 (3)	0.32235 (19)	0.0336 (6)
C33	0.5523 (4)	−0.0216 (3)	0.3823 (2)	0.0218 (6)
C34	0.3859 (4)	−0.0339 (4)	0.3937 (2)	0.0246 (7)
C35	0.2509 (4)	0.0741 (4)	0.4027 (2)	0.0250 (7)
C36	0.2832 (4)	0.1924 (3)	0.4020 (2)	0.0231 (7)
C41	0.2796 (4)	0.5121 (3)	0.3080 (2)	0.0208 (6)
C42	0.1545 (4)	0.6315 (3)	0.3003 (2)	0.0217 (6)
I42	0.05593 (3)	0.71566 (2)	0.413668 (17)	0.03445 (9)
C43	0.0967 (4)	0.6963 (4)	0.2184 (3)	0.0286 (7)
C44	0.1630 (5)	0.6451 (4)	0.1420 (3)	0.0320 (8)
C45	0.2878 (5)	0.5286 (4)	0.1476 (2)	0.0316 (8)
C46	0.3450 (5)	0.4626 (3)	0.2298 (2)	0.0263 (7)
H1	0.5567	0.2679	0.9458	0.034*
H171	0.3875	0.2053	0.8307	0.029*
H172	0.5313	0.2861	0.8018	0.029*
H13	0.0745	0.6171	0.6706	0.035*
H14	−0.0501	0.7207	0.7911	0.041*
H15	0.0371	0.6270	0.9336	0.039*
H16	0.2454	0.4322	0.9543	0.031*
H23	0.3959	0.0383	1.2173	0.040*
H24	0.1475	−0.0228	1.1944	0.042*
H25	0.0520	0.0444	1.0568	0.042*
H26	0.1922	0.1628	0.9379	0.035*
H3	0.2745	0.4723	0.4383	0.032*
H371	0.5236	0.3304	0.4565	0.029*
H372	0.5734	0.3566	0.3504	0.029*
H33	0.6457	−0.0936	0.3735	0.026*
H34	0.3637	−0.1158	0.3954	0.030*
H35	0.1361	0.0665	0.4093	0.030*
H36	0.1893	0.2656	0.4066	0.028*
H43	0.0114	0.7759	0.2151	0.034*
H44	0.1236	0.6891	0.0861	0.038*
H45	0.3348	0.4936	0.0951	0.038*
H46	0.4297	0.3827	0.2325	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0193 (13)	0.0414 (17)	0.0235 (14)	−0.0077 (12)	−0.0080 (11)	0.0012 (13)
C17	0.0230 (16)	0.0265 (16)	0.0205 (16)	−0.0006 (13)	−0.0066 (12)	−0.0024 (13)
C11	0.0189 (14)	0.0200 (14)	0.0232 (16)	−0.0051 (12)	−0.0058 (12)	−0.0049 (12)
C12	0.0213 (15)	0.0209 (15)	0.0231 (16)	−0.0073 (12)	−0.0061 (12)	−0.0035 (12)
N12	0.0417 (18)	0.0287 (15)	0.0229 (15)	−0.0172 (14)	−0.0128 (13)	0.0009 (12)
O11	0.070 (2)	0.0406 (17)	0.0346 (16)	0.0090 (16)	−0.0134 (15)	−0.0205 (14)
O12	0.098 (3)	0.0430 (18)	0.0224 (14)	−0.0192 (18)	−0.0194 (16)	−0.0001 (13)
C13	0.0209 (16)	0.0243 (16)	0.042 (2)	−0.0069 (13)	−0.0117 (14)	0.0045 (15)
C14	0.0198 (16)	0.0217 (16)	0.057 (3)	−0.0005 (13)	−0.0024 (16)	−0.0069 (17)
C15	0.0274 (18)	0.0295 (18)	0.044 (2)	−0.0101 (15)	0.0090 (16)	−0.0193 (17)
C16	0.0236 (16)	0.0302 (17)	0.0247 (16)	−0.0074 (14)	−0.0013 (13)	−0.0091 (14)
C21	0.0153 (14)	0.0238 (16)	0.0247 (16)	0.0005 (12)	−0.0037 (12)	−0.0028 (13)
C22	0.0210 (15)	0.0258 (16)	0.0230 (16)	0.0014 (13)	−0.0012 (12)	−0.0075 (13)
I22	0.02431 (14)	0.05411 (18)	0.02607 (14)	−0.00191 (11)	−0.00718 (9)	−0.01675 (11)
C23	0.038 (2)	0.0326 (19)	0.0234 (17)	−0.0010 (16)	0.0017 (15)	−0.0045 (15)
C24	0.0334 (19)	0.0206 (16)	0.036 (2)	−0.0016 (14)	0.0201 (16)	0.0017 (15)
C25	0.0237 (17)	0.0289 (18)	0.051 (2)	−0.0054 (14)	0.0058 (16)	−0.0146 (17)
C26	0.0204 (16)	0.0335 (19)	0.0340 (19)	−0.0045 (14)	−0.0046 (14)	−0.0080 (15)
N3	0.0313 (15)	0.0228 (14)	0.0195 (14)	0.0071 (12)	−0.0050 (11)	−0.0048 (11)
C37	0.0220 (15)	0.0208 (15)	0.0263 (17)	0.0015 (12)	−0.0056 (13)	−0.0045 (13)
C31	0.0162 (14)	0.0221 (15)	0.0152 (14)	−0.0005 (12)	−0.0025 (11)	−0.0005 (11)
C32	0.0120 (13)	0.0239 (15)	0.0163 (14)	−0.0018 (11)	−0.0036 (10)	−0.0007 (12)
N32	0.0140 (12)	0.0222 (13)	0.0235 (13)	0.0009 (10)	−0.0037 (10)	0.0021 (11)
O31	0.0215 (12)	0.0320 (13)	0.0367 (14)	−0.0072 (10)	−0.0097 (10)	−0.0031 (11)
O32	0.0179 (12)	0.0384 (15)	0.0380 (15)	0.0022 (10)	0.0017 (10)	−0.0090 (12)
C33	0.0213 (15)	0.0221 (15)	0.0184 (15)	−0.0009 (12)	−0.0052 (12)	0.0004 (12)
C34	0.0241 (16)	0.0288 (17)	0.0214 (16)	−0.0077 (13)	−0.0053 (13)	−0.0024 (13)
C35	0.0173 (15)	0.0350 (18)	0.0216 (15)	−0.0074 (13)	−0.0056 (12)	0.0007 (14)
C36	0.0147 (14)	0.0287 (16)	0.0198 (15)	0.0036 (12)	−0.0022 (11)	−0.0030 (13)
C41	0.0198 (14)	0.0200 (15)	0.0229 (16)	−0.0045 (12)	−0.0042 (12)	−0.0039 (12)
C42	0.0173 (14)	0.0207 (15)	0.0267 (16)	−0.0055 (12)	−0.0043 (12)	−0.0015 (13)
I42	0.03699 (15)	0.02458 (14)	0.03448 (16)	0.00676 (10)	−0.00210 (11)	−0.00978 (10)
C43	0.0210 (16)	0.0293 (17)	0.0341 (19)	−0.0097 (14)	−0.0095 (14)	0.0058 (15)
C44	0.0295 (18)	0.043 (2)	0.0264 (18)	−0.0173 (16)	−0.0131 (14)	0.0054 (16)
C45	0.037 (2)	0.042 (2)	0.0212 (17)	−0.0180 (17)	−0.0035 (14)	−0.0057 (15)
C46	0.0306 (18)	0.0271 (17)	0.0218 (16)	−0.0073 (14)	−0.0031 (13)	−0.0050 (13)

Geometric parameters (Å, º)

N1—C21	1.371 (4)	N3—C41	1.376 (4)
N1—C17	1.448 (4)	N3—C37	1.445 (4)
N1—H1	0.88	N3—H3	0.88
C17—C11	1.531 (4)	C37—C31	1.523 (5)
C17—H171	0.99	C37—H371	0.99
C17—H172	0.99	C37—H372	0.99
C11—C16	1.387 (5)	C31—C36	1.395 (4)
C11—C12	1.409 (4)	C31—C32	1.397 (4)
C12—C13	1.390 (5)	C32—C33	1.390 (5)
C12—N12	1.487 (5)	C32—N32	1.473 (4)
N12—O11	1.198 (4)	N32—O32	1.219 (4)
N12—O12	1.214 (4)	N32—O31	1.235 (4)
C13—C14	1.375 (6)	C33—C34	1.379 (5)
C13—H13	0.95	C33—H33	0.95
C14—C15	1.394 (6)	C34—C35	1.390 (5)
C14—H14	0.95	C34—H34	0.95
C15—C16	1.394 (5)	C35—C36	1.381 (5)
C15—H15	0.95	C35—H35	0.95
C16—H16	0.95	C36—H36	0.95
C21—C22	1.397 (5)	C41—C46	1.396 (5)
C21—C26	1.412 (5)	C41—C42	1.413 (4)
C22—C23	1.380 (5)	C42—C43	1.393 (5)
C22—I22	2.110 (4)	C42—I42	2.095 (4)
C23—C24	1.434 (6)	C43—C44	1.382 (6)
C23—H23	0.95	C43—H43	0.95
C24—C25	1.340 (6)	C44—C45	1.390 (6)
C24—H24	0.95	C44—H44	0.95
C25—C26	1.389 (6)	C45—C46	1.398 (5)
C25—H25	0.95	C45—H45	0.95
C26—H26	0.95	C46—H46	0.95
C21—N1—C17	123.8 (3)	C41—N3—C37	123.2 (3)
C21—N1—H1	118.1	C41—N3—H3	118.4
C17—N1—H1	118.1	C37—N3—H3	118.4
N1—C17—C11	113.2 (3)	N3—C37—C31	114.6 (3)
N1—C17—H171	108.9	N3—C37—H371	108.6
C11—C17—H171	108.9	C31—C37—H371	108.6
N1—C17—H172	108.9	N3—C37—H372	108.6
C11—C17—H172	108.9	C31—C37—H372	108.6
H171—C17—H172	107.7	H371—C37—H372	107.6
C16—C11—C12	115.6 (3)	C36—C31—C32	115.8 (3)
C16—C11—C17	119.9 (3)	C36—C31—C37	121.2 (3)
C12—C11—C17	124.5 (3)	C32—C31—C37	123.0 (3)
C13—C12—C11	123.0 (3)	C33—C32—C31	123.2 (3)
C13—C12—N12	116.2 (3)	C33—C32—N32	116.2 (3)
C11—C12—N12	120.8 (3)	C31—C32—N32	120.6 (3)
O11—N12—O12	123.8 (4)	O32—N32—O31	124.2 (3)
O11—N12—C12	119.1 (3)	O32—N32—C32	117.9 (3)
O12—N12—C12	117.0 (3)	O31—N32—C32	117.8 (3)
C14—C13—C12	119.6 (4)	C34—C33—C32	119.0 (3)
C14—C13—H13	120.2	C34—C33—H33	120.5
C12—C13—H13	120.2	C32—C33—H33	120.5
C13—C14—C15	119.3 (3)	C33—C34—C35	119.6 (3)
C13—C14—H14	120.3	C33—C34—H34	120.2
C15—C14—H14	120.3	C35—C34—H34	120.2
C16—C15—C14	120.0 (4)	C36—C35—C34	120.2 (3)
C16—C15—H15	120.0	C36—C35—H35	119.9
C14—C15—H15	120.0	C34—C35—H35	119.9
C11—C16—C15	122.4 (3)	C35—C36—C31	122.2 (3)
C11—C16—H16	118.8	C35—C36—H36	118.9
C15—C16—H16	118.8	C31—C36—H36	118.9
N1—C21—C22	121.8 (3)	N3—C41—C46	121.4 (3)
N1—C21—C26	122.1 (3)	N3—C41—C42	121.3 (3)
C22—C21—C26	116.1 (3)	C46—C41—C42	117.2 (3)
C23—C22—C21	122.8 (3)	C43—C42—C41	121.5 (3)
C23—C22—I22	117.5 (3)	C43—C42—I42	118.8 (3)
C21—C22—I22	119.7 (3)	C41—C42—I42	119.6 (2)
C22—C23—C24	119.3 (4)	C44—C43—C42	120.2 (3)
C22—C23—H23	120.4	C44—C43—H43	119.9
C24—C23—H23	120.4	C42—C43—H43	119.9
C25—C24—C23	118.2 (3)	C43—C44—C45	119.4 (3)
C25—C24—H24	120.9	C43—C44—H44	120.3
C23—C24—H24	120.9	C45—C44—H44	120.3
C24—C25—C26	122.7 (4)	C44—C45—C46	120.6 (4)
C24—C25—H25	118.6	C44—C45—H45	119.7
C26—C25—H25	118.6	C46—C45—H45	119.7
C25—C26—C21	120.9 (4)	C41—C46—C45	121.1 (3)
C25—C26—H26	119.6	C41—C46—H46	119.5
C21—C26—H26	119.6	C45—C46—H46	119.5
C21—N1—C17—C11	86.5 (4)	C41—N3—C37—C31	−81.6 (4)
N1—C17—C11—C16	−3.0 (4)	N3—C37—C31—C36	−13.5 (4)
N1—C17—C11—C12	174.7 (3)	N3—C37—C31—C32	166.4 (3)
C16—C11—C12—C13	−0.5 (5)	C36—C31—C32—C33	−1.6 (5)
C17—C11—C12—C13	−178.3 (3)	C37—C31—C32—C33	178.5 (3)
C16—C11—C12—N12	178.8 (3)	C36—C31—C32—N32	178.2 (3)
C17—C11—C12—N12	1.0 (5)	C37—C31—C32—N32	−1.7 (5)
C13—C12—N12—O11	−166.2 (4)	C33—C32—N32—O32	35.8 (4)
C11—C12—N12—O11	14.5 (5)	C31—C32—N32—O32	−144.0 (3)
C13—C12—N12—O12	13.3 (5)	C33—C32—N32—O31	−143.7 (3)
C11—C12—N12—O12	−166.0 (3)	C31—C32—N32—O31	36.5 (4)
C11—C12—C13—C14	0.1 (5)	C31—C32—C33—C34	−1.2 (5)
N12—C12—C13—C14	−179.2 (3)	N32—C32—C33—C34	179.0 (3)
C12—C13—C14—C15	0.2 (5)	C32—C33—C34—C35	2.7 (5)
C13—C14—C15—C16	−0.2 (5)	C33—C34—C35—C36	−1.3 (5)
C12—C11—C16—C15	0.6 (5)	C34—C35—C36—C31	−1.7 (5)
C17—C11—C16—C15	178.5 (3)	C32—C31—C36—C35	3.0 (5)
C14—C15—C16—C11	−0.3 (5)	C37—C31—C36—C35	−177.1 (3)
C17—N1—C21—C22	175.2 (3)	C37—N3—C41—C46	12.5 (5)
C17—N1—C21—C26	−6.0 (5)	C37—N3—C41—C42	−168.2 (3)
N1—C21—C22—C23	179.7 (3)	N3—C41—C42—C43	−178.4 (3)
C26—C21—C22—C23	0.8 (5)	C46—C41—C42—C43	1.0 (5)
N1—C21—C22—I22	0.0 (5)	N3—C41—C42—I42	2.8 (4)
C26—C21—C22—I22	−178.9 (2)	C46—C41—C42—I42	−177.9 (2)
C21—C22—C23—C24	0.4 (6)	C41—C42—C43—C44	−0.8 (5)
I22—C22—C23—C24	−179.9 (3)	I42—C42—C43—C44	178.1 (3)
C22—C23—C24—C25	−1.4 (5)	C42—C43—C44—C45	−0.1 (5)
C23—C24—C25—C26	1.2 (6)	C43—C44—C45—C46	0.8 (5)
C24—C25—C26—C21	0.1 (6)	N3—C41—C46—C45	179.0 (3)
N1—C21—C26—C25	−179.9 (3)	C42—C41—C46—C45	−0.3 (5)
C22—C21—C26—C25	−1.1 (5)	C44—C45—C46—C41	−0.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O12	0.88	2.34	3.107 (4)	146
C33—H33···O11^i	0.95	2.53	3.147 (5)	123

Symmetry code: (i) −x+1, −y, −z+1.

 

Footnotes

‡Postal address: School of Engineering and Physics, University of Dundee, Dundee DD1 4HN, Scotland

§Present address: Fundação Oswaldo Cruz, Far Manguinhos, Rua Sizenando Nabuco, 100 Manguinhos, 21041250 Rio de Janeiro, RJ Brazil.

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: NA5018 ). Services for accessing these data are described at the back of the journal.