Hydro­gen-bonded chains of rings in 3-iodo­benz­aldehyde 2,4-di­nitro­phenyl­hydrazone and 4-iodo­benz­aldehyde 2,4-di­nitro­phenyl­hydrazone, and a three-dimensional framework in 4-iodo­benz­aldehyde 4-nitro­phenyl­hydrazone generated by the combi­nation of N-H...O and C-H...O hydrogen bonds with iodo-nitro interactions

Molecules of 3- and 4-iodo­benz­aldehyde 2,4-di­nitro­phenyl­hydrazone, C₁₃H₉IN₄O₄, are both effectively planar. In the crystal structure of each compound, molecules are linked by a combination of N-H...O and C-H...O hydrogen bonds into complex chains of rings, containing four and three different ring motifs, respectively; neither compound contains any iodo-nitro interactions. In 3-iodo­benz­aldehyde 4-nitro­phenyl­hydrazone, C₁₃H₁₀IN₃O₂, where the iodinated aryl ring is disordered over two sets of sites, the hydrogen bonds generate a chain of rings, while two independent I...O interactions generate a three-dimensional framework.

S1. Comment

We report here the molecular and supramolecular structures of the title compounds, (I)–(III), and we compare their supramolecular behaviours with those of the related compounds (IV) and (V), which we reported recently (Glidewell et al., 2003). In no two of these compounds does the interplay of hard and soft hydrogen bonds with the iodo–nitro interactions generate the same pattern of supramolecular aggregation.

The molecules of (I)–(III) are all nearly planar, as shown by the key torsional angles (Tables 1,3 and 5); the sole exception concerns the minor orientation of the iodinated ring in (III). The bond distances and interbond angles present no unusual features and the principal structural interest lies in the intermolecular interactions and their consequences.

Although the isomeric compounds (I) and (II) both crystallize in space group C2/c, they have very different unit-cell dimensions (see Experimental). However, we discuss the supramolecular structures of these two compounds together, as they have a number of features in common.

There are neither iodo–nitro interactions nor aromatic π···π stacking interactions in the structures of (I) and (II), and N—H···π(arene) and C—H···π(arene) hydrogen bonds are also absent from both. Instead, the supramolecular structure of both compounds is determined by a three-centre N—H···(O)₂ hydrogen bond, augmented by two-centre C—H···O hydrogen bonds (Tables 2 and 4). While the effect of the three-centre interaction is identical in (I) and (II), the effect of the C—H···O hydrogen bonds is different in the two compounds, and it is this difference that generates their different overall structures. In both compounds, however, the dominant C—H···O hydrogen bond involves the C—H bond that lies between the two nitro groups and which may therefore be expected to be the most acidic C—H bond in the molecule.

In both compounds (Figs. 1 and 2), hydrazone atom N2 acts as a donor in a three-centre hydrogen bond, in which the two acceptors are, firstly, atom O21 in the same molecule at (x, y, z), giving rise to an S(6) motif (Bernstein et al., 1995), and secondly, atom O21 in the molecule at (1 − x, 1 − y, 1 − z), producing a centrosymmetric dimer centred at (1/2, 1/2, 1/2), which contains an unusual sequence of three fused rings with graph-set descriptor S(6)R²₂(4)S(6) (Fig. 3). In both compounds, these dimeric aggregates are linked into chains by a single C—H···O hydrogen bond, but in (I), the chain is generated by translation, while in (II) it is generated by the action of a twofold rotation axis.

In (I), atom C13 in the molecule at (x, y, z), which is a component of the dimer centred at (1/2, 1/2, 1/2), acts as hydrogen-bond donor to nitro atom O41 in the molecule at (1 − x, −2 − y, 1 − z), which is a component of the dimer centred at (1/2, 1.5, 1/2), so forming an R²₂(10) motif (Fig. 3). Propagation of this single interaction by inversion and translation then generates a chain of rings running parallel to the [010] direction. This chain is further reinforced, albeit rather weakly, by a second C—H···O hydrogen bond, in which atom C5 at (x, y, z) acts as a donor to nitro atom O42 in the molecule at (x, −1 + y, z), which is a component of the dimer centred at (1/2, −0.5, 1/2), so completing the formation of a continuous chain of edge-fused rings containing four different types of ring, namely S(6), R²₂(4), R²₂(10) and R³₃(16) (Fig. 3). This nearly-planar structure can alternatively be regarded as a multiply perforated ribbon.

In (II), by contrast, atom C13 in the molecule at (x, y, z), itself a component of the R²₂(4) dimer centred at (1/2, 1/2, 1/2), acts as a hydrogen-bond donor to nitro atom O41 in the molecule at (1 − x, y, 0.5 − z), which is a component of the dimer centred at (1/2, 1/2, 0). In turn, atom C13 at (1 − x, y, 0.5 − z) acts as a donor to atom O4 at (x, y, z), so that the R²₂(10) motif in this compound is generated by the twofold rotation axis along (1/2, y, 1/4). Propagation of this single C—H···O hydrogen bond then generates, by rotation and inversion, a deeply folded chain of rings running parallel to the [001] direction and containing three distinct types of ring (Fig. 4). The iodophenyl ring plays no part in the supramolecular aggregation.

The supramolecular structures of (I) and (II) (Figs 3 and 4) may be contrasted with that of the isomeric 2-iodobenzaldehyde-2,4-dinitrophenylhydrazone, (IV) (Glidewell et al., 2003). In the crystal structure of (IV), the whole molecule is disordered over two sets of sites; for the major orientation, there are no direction-specific interactions between the molecules, while for the minor orientation, a single C—H···O hydrogen bond generates centrosymmetric R²₂(10) dimers. As in (I) and (II), it is the C—H bond between the two nitro groups that is involved.

In (III), the molecules (Fig. 5) are linked into a zigzag chain of rings by means of a cooperative combination of N—H···O and C—H···O hydrogen bonds (Table 6). Hydrazone atom N2 and aryl atom C16 in the molecule at (x, y, z) act as hydrogen-bond donors to nitro atoms O42 and O41, respectively, in the molecule at (1 + x, 1 − y, −0.5 + z), so producing a C(6) C(8)[R²₂(8)] chain of rings running parallel to the [20–1] direction and generated by the c-glide plane at y = 0.5 (Fig. 6). A second such chain, related to the first by the C-centring operation, is generated by the c-glide plane at y = 0, but there are neither X—H···π(arene) hydrogen bonds (X = C or N) nor aromatic π···π stacking interactions between or within the chains.

There are, however, two long two-centre iodo–nitro interactions between the molecules. Atom I4 in the molecule at (x, y, z) makes contacts with nitro atom O41 in the molecule at (1.5 + x, 0.5 − y, −0.5 + z) [I···O = 3.537 (4) Å and C—I···O = 142.9 (2)°], and with nitro atom O42 in the molecule at (1.5 + x, −0.5 + y, z) [I···O = 3.525 (4) Å and C—I···O = 140.4 (2)°]. If these two interactions are regarded as structurally significant then it is a straightforward matter to show that they generate a continuous three-dimensional structure, independent of the contribution of the hydrogen bonding. The two I···O interactions individually generate C(14) chains (Starbuck et al., 1999) running parallel to the [30–1] and [3–10] directions, respectively (Fig. 7). In addition, the action of the glide planes generates chains running parallel to the [310] direction. Finally, the combination of the two interactions together generates a chain running parallel to the [010] direction (Fig. C3). Atom I4 in the molecule at (1.5 + x, 0.5 − y, −0.5 + z) makes an I···O contact with atom O42 at (3 + x, 1 − y, −0.5 + z), while atom O41 in this molecule at (3 + x, 1 − y, −0.5 + z) makes an I···O contact with atom I4 in the molecule at (1.5 + x, 0.5 + y, z), which is in turn directly linked to the molecule at (x, 1 + y, z), so generating a C²₂(28) chain parallel to [010] (Fig. 7). The combination of the [10], [310], [31–0] and [30–1] iodo–nitro chains is sufficient to generate a three-dimensional framework.

In 2-iodobenzaldehyde-4-nitrophenylhydrazone, (V) (Glidewell et al., 2003), an isomer of (III), a combination of an N—H···O hydrogen bond and a single two-centre iodo–nitro interaction link the molecules into a chain of edge-fused R³₃(18) rings. It is unfortunate that we cannot discuss here the supramolecular structure of the further isomer 3-iodobenzaldehyde-4-nitrophenylhydrazone, but repeated attempts to prepare this compound in pure crystalline form have been unsuccessful.

S2. Experimental

For the preparation of each of (I)–(III), a finely powdered mixture of the appropriate iodobenzaldehyde and the appropriate phenylhydrazine (1:1 molar ratio) was gently heated on a hotplate until effervescence ceased. The mixtures were cooled and recrystallized from ethanol.

S3. Refinement

Crystals of (I)–(III) are all monoclinic, and for each compound, the systematic absences permitted C2/c and Cc as possible space groups. Space group C2/c was chosen for (I) and (II), and Cc was chosen for (III); these selections were all confirmed by the subsequent structural analyses. In (III), the C—H units of the iodinated ring were disordered over two sets of sites, having occupancies of 0.545 (12) (CnA; n = 2, 3, 5, 6) and 0.455 (12) (CnB); the disordered C atoms were all refined isotropically. A data set for (III) collected at 120 (2) K provided no tractable solution, but in the 291 (2) K data set, only ca 42% of the reflection are labelled observed. All H atoms were treated as riding atoms, with C—H distances of 0.95 Å and N—H distances of 0.88 Å for (I) and (II) at 120 (2) K, and C—H distances of 0.93 Å and N—H distances of 0.86 Å for (III) at 291 (2) K. For (III), the correct orientation of the structure relative to the directions of the polar axes was established by means of the Flack (1983) parameter.

Computing details

For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1986) for (I); SHELXS97 (Sheldrick, 1997) for (II), (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a continuous chain of edge-fused rings running along [010].
	Fig. 4. A stereoview of part of the crystal structure of (II), showing the formation of a chain of rings running along [001].
	Fig. 5. The molecule of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. For the sake of clarity, only the major orientation of the disordered aryl ring (C1–C6) is shown.
	Fig. 6. Part of the crystal structure of (III), showing the formation of a hydrogen-bonded chain of rings along [20–1]. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 + x, 1 − y, −0.5 + z) and (−1 + x, 1 − y, 0.5 + z), respectively.
	Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of iodo–nitro chains along [010], [3–10] and [30–1].

(I) 3-Iodobenzaldehyde 2,4-dinitrophenylhydrazone

Crystal data

C13H9IN4O4	F(000) = 1600
Mr = 412.14	Dx = 1.950 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3220 reflections
a = 30.0604 (9) Å	θ = 3.0–27.5°
b = 13.5628 (4) Å	µ = 2.31 mm^−1
c = 7.0263 (2) Å	T = 120 K
β = 101.390 (2)°	Plate, colourless
V = 2808.23 (14) Å^3	0.45 × 0.25 × 0.02 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	3220 independent reflections
Radiation source: fine-focus sealed X-ray tube	2545 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −38→38
Tmin = 0.424, Tmax = 0.955	k = −17→15
17244 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.070	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 3.2981P] where P = (Fo^2 + 2Fc^2)/3
3220 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.77 e Å^−3
0 restraints	Δρmin = −1.32 e Å^−3

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

	x	y	z	Uiso*/Ueq
C1	0.35503 (10)	0.3679 (2)	0.0683 (4)	0.0193 (6)
C2	0.32014 (9)	0.4107 (2)	−0.0681 (4)	0.0176 (6)
C3	0.28676 (10)	0.3515 (2)	−0.1728 (4)	0.0203 (6)
C4	0.28660 (10)	0.2499 (2)	−0.1444 (4)	0.0245 (6)
C5	0.32147 (10)	0.2077 (2)	−0.0105 (4)	0.0243 (7)
C6	0.35547 (9)	0.2660 (2)	0.0953 (4)	0.0202 (6)
I3	0.235428 (7)	0.416977 (15)	−0.38017 (3)	0.02955 (9)
C7	0.39109 (9)	0.4280 (2)	0.1802 (4)	0.0193 (6)
N1	0.39107 (8)	0.52185 (17)	0.1563 (3)	0.0185 (5)
N2	0.42639 (8)	0.57186 (16)	0.2699 (3)	0.0180 (5)
C11	0.42588 (9)	0.6719 (2)	0.2686 (4)	0.0173 (6)
C12	0.45939 (9)	0.7305 (2)	0.3869 (4)	0.0183 (6)
C13	0.45722 (10)	0.8335 (2)	0.3849 (4)	0.0206 (6)
C14	0.42178 (10)	0.8776 (2)	0.2626 (4)	0.0223 (6)
C15	0.38841 (10)	0.8231 (2)	0.1417 (4)	0.0225 (6)
C16	0.39035 (10)	0.7231 (2)	0.1454 (4)	0.0204 (6)
N12	0.49819 (8)	0.68813 (17)	0.5144 (3)	0.0192 (5)
O21	0.50056 (7)	0.59664 (14)	0.5290 (3)	0.0295 (5)
O22	0.52784 (6)	0.74225 (15)	0.6024 (3)	0.0250 (4)
N14	0.41871 (9)	0.98532 (19)	0.2623 (4)	0.0308 (6)
O41	0.44907 (8)	1.03224 (16)	0.3626 (4)	0.0410 (6)
O42	0.38513 (8)	1.02313 (17)	0.1593 (4)	0.0431 (6)
H2	0.3195	0.4800	−0.0884	0.021*
H4	0.2630	0.2102	−0.2155	0.029*
H5	0.3221	0.1383	0.0088	0.029*
H6	0.3792	0.2364	0.1868	0.024*
H7	0.4147	0.3977	0.2712	0.023*
H2A	0.4490	0.5395	0.3422	0.022*
H13	0.4797	0.8717	0.4664	0.025*
H15	0.3644	0.8557	0.0570	0.027*
H16	0.3673	0.6864	0.0632	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0178 (14)	0.0209 (15)	0.0194 (14)	−0.0009 (12)	0.0045 (11)	−0.0007 (11)
C2	0.0177 (14)	0.0164 (14)	0.0182 (14)	−0.0001 (11)	0.0026 (11)	0.0004 (11)
C3	0.0171 (14)	0.0256 (16)	0.0171 (14)	−0.0014 (12)	0.0009 (11)	−0.0017 (12)
C4	0.0253 (16)	0.0211 (15)	0.0256 (15)	−0.0057 (13)	0.0018 (12)	−0.0062 (13)
C5	0.0251 (16)	0.0188 (15)	0.0296 (17)	−0.0018 (12)	0.0067 (13)	−0.0003 (12)
C6	0.0191 (14)	0.0193 (15)	0.0218 (14)	0.0008 (12)	0.0031 (11)	−0.0009 (12)
I3	0.02467 (13)	0.03447 (14)	0.02449 (12)	−0.00515 (9)	−0.00737 (8)	0.00252 (9)
C7	0.0137 (14)	0.0249 (16)	0.0184 (14)	0.0005 (12)	0.0013 (11)	−0.0016 (12)
N1	0.0150 (12)	0.0221 (13)	0.0173 (11)	−0.0015 (10)	0.0000 (9)	−0.0038 (10)
N2	0.0135 (12)	0.0187 (13)	0.0191 (12)	−0.0001 (10)	−0.0036 (9)	−0.0004 (10)
C11	0.0178 (14)	0.0176 (14)	0.0165 (13)	−0.0002 (11)	0.0030 (11)	−0.0015 (11)
C12	0.0156 (14)	0.0208 (15)	0.0177 (13)	0.0008 (11)	0.0009 (10)	−0.0006 (11)
C13	0.0195 (15)	0.0209 (15)	0.0203 (14)	0.0008 (12)	0.0016 (11)	−0.0005 (12)
C14	0.0215 (16)	0.0185 (14)	0.0253 (15)	0.0015 (12)	0.0005 (12)	0.0002 (12)
C15	0.0170 (15)	0.0241 (16)	0.0244 (15)	0.0058 (12)	−0.0007 (11)	0.0019 (12)
C16	0.0177 (14)	0.0221 (16)	0.0197 (14)	−0.0017 (12)	−0.0004 (11)	−0.0009 (11)
N12	0.0167 (12)	0.0205 (13)	0.0187 (12)	0.0002 (10)	−0.0005 (9)	−0.0013 (10)
O21	0.0294 (12)	0.0145 (11)	0.0376 (13)	0.0030 (9)	−0.0105 (10)	−0.0016 (9)
O22	0.0175 (10)	0.0239 (11)	0.0294 (11)	−0.0037 (9)	−0.0060 (8)	−0.0025 (9)
N14	0.0298 (15)	0.0200 (14)	0.0397 (16)	0.0056 (12)	−0.0002 (12)	0.0027 (12)
O41	0.0392 (15)	0.0197 (12)	0.0572 (16)	−0.0043 (11)	−0.0072 (12)	−0.0040 (11)
O42	0.0432 (15)	0.0247 (13)	0.0537 (16)	0.0128 (11)	−0.0091 (12)	0.0037 (11)

Geometric parameters (Å, º)

C1—C6	1.394 (4)	N2—H2A	0.88
C1—C2	1.400 (4)	C11—C16	1.416 (4)
C1—C7	1.457 (4)	C11—C12	1.417 (4)
C2—C3	1.378 (4)	C12—C13	1.397 (4)
C2—H2	0.95	C12—N12	1.442 (3)
C3—C4	1.393 (4)	C13—C14	1.367 (4)
C3—I3	2.099 (3)	C13—H13	0.95
C4—C5	1.386 (4)	C14—C15	1.392 (4)
C4—H4	0.95	C14—N14	1.464 (4)
C5—C6	1.387 (4)	C15—C16	1.358 (4)
C5—H5	0.95	C15—H15	0.95
C6—H6	0.95	C16—H16	0.95
C7—N1	1.284 (4)	N12—O22	1.224 (3)
C7—H7	0.95	N12—O21	1.246 (3)
N1—N2	1.375 (3)	N14—O41	1.217 (3)
N2—C11	1.357 (3)	N14—O42	1.232 (3)
C6—C1—C2	119.4 (3)	N2—C11—C16	120.0 (2)
C6—C1—C7	119.7 (3)	N2—C11—C12	123.5 (2)
C2—C1—C7	121.0 (3)	C16—C11—C12	116.5 (2)
C3—C2—C1	119.5 (3)	C13—C12—C11	121.9 (2)
C3—C2—H2	120.3	C13—C12—N12	115.8 (2)
C1—C2—H2	120.3	C11—C12—N12	122.3 (2)
C2—C3—C4	121.5 (3)	C14—C13—C12	118.2 (3)
C2—C3—I3	118.8 (2)	C14—C13—H13	120.9
C4—C3—I3	119.7 (2)	C12—C13—H13	120.9
C5—C4—C3	118.8 (3)	C13—C14—C15	122.0 (3)
C5—C4—H4	120.6	C13—C14—N14	118.6 (3)
C3—C4—H4	120.6	C15—C14—N14	119.4 (2)
C4—C5—C6	120.5 (3)	C16—C15—C14	119.7 (3)
C4—C5—H5	119.8	C16—C15—H15	120.1
C6—C5—H5	119.8	C14—C15—H15	120.1
C5—C6—C1	120.4 (3)	C15—C16—C11	121.7 (3)
C5—C6—H6	119.8	C15—C16—H16	119.2
C1—C6—H6	119.8	C11—C16—H16	119.2
N1—C7—C1	120.2 (3)	O22—N12—O21	122.1 (2)
N1—C7—H7	119.9	O22—N12—C12	119.6 (2)
C1—C7—H7	119.9	O21—N12—C12	118.3 (2)
C7—N1—N2	115.7 (2)	O41—N14—O42	123.8 (3)
C11—N2—N1	118.9 (2)	O41—N14—C14	118.8 (2)
C11—N2—H2A	120.6	O42—N14—C14	117.4 (2)
N1—N2—H2A	120.6
C6—C1—C2—C3	0.2 (4)	C16—C11—C12—N12	−177.9 (2)
C7—C1—C2—C3	179.4 (3)	C11—C12—C13—C14	−0.8 (4)
C1—C2—C3—C4	0.8 (4)	N12—C12—C13—C14	178.2 (2)
C1—C2—C3—I3	−178.9 (2)	C12—C13—C14—C15	−0.1 (4)
C2—C3—C4—C5	−1.4 (4)	C12—C13—C14—N14	178.8 (3)
I3—C3—C4—C5	178.3 (2)	C13—C14—C15—C16	0.8 (5)
C3—C4—C5—C6	1.0 (4)	N14—C14—C15—C16	−178.1 (3)
C4—C5—C6—C1	−0.1 (4)	C14—C15—C16—C11	−0.6 (5)
C2—C1—C6—C5	−0.6 (4)	N2—C11—C16—C15	179.3 (3)
C7—C1—C6—C5	−179.8 (3)	C12—C11—C16—C15	−0.4 (4)
C6—C1—C7—N1	179.9 (3)	C13—C12—N12—O22	−4.5 (4)
C2—C1—C7—N1	0.7 (4)	C11—C12—N12—O22	174.6 (2)
C1—C7—N1—N2	179.6 (2)	C13—C12—N12—O21	176.4 (3)
C7—N1—N2—C11	−172.6 (3)	C11—C12—N12—O21	−4.5 (4)
N1—N2—C11—C16	−2.7 (4)	C13—C14—N14—O41	4.1 (4)
N1—N2—C11—C12	176.9 (2)	C15—C14—N14—O41	−177.0 (3)
N2—C11—C12—C13	−178.5 (3)	C13—C14—N14—O42	−175.9 (3)
C16—C11—C12—C13	1.1 (4)	C15—C14—N14—O42	3.1 (4)
N2—C11—C12—N12	2.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O21	0.88	1.98	2.607 (3)	127
N2—H2A···O21^i	0.88	2.45	3.289 (3)	160

Symmetry code: (i) −x+1, −y+1, −z+1.

(II) 4-Iodobenzaldehyde 2,4-dinitrophenylhydrazone

Crystal data

C13H9IN4O4	F(000) = 1600
Mr = 412.14	Dx = 2.002 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3074 reflections
a = 32.359 (2) Å	θ = 3.2–27.6°
b = 4.6293 (3) Å	µ = 2.37 mm^−1
c = 18.4169 (15) Å	T = 120 K
β = 97.631 (3)°	Needle, orange
V = 2734.4 (3) Å^3	0.45 × 0.04 × 0.02 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	3074 independent reflections
Radiation source: fine-focus sealed X-ray tube	1686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.118
ϕ scans, and ω scans with κ offsets	θmax = 27.6°, θmin = 3.2°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −41→40
Tmin = 0.416, Tmax = 0.954	k = −5→6
12789 measured reflections	l = −23→19

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0235P)^2] where P = (Fo^2 + 2Fc^2)/3
3074 reflections	(Δ/σ)max = 0.002
199 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −1.09 e Å^−3

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

	x	y	z	Uiso*/Ueq
C1	0.64812 (15)	0.1563 (13)	0.5656 (3)	0.0175 (12)
C2	0.68385 (16)	0.1696 (13)	0.5303 (3)	0.0252 (13)
C3	0.71950 (16)	0.0187 (12)	0.5565 (3)	0.0244 (14)
C4	0.71927 (15)	−0.1527 (13)	0.6195 (3)	0.0209 (12)
I4	0.775212 (12)	−0.34687 (10)	0.66469 (2)	0.03486 (15)
C5	0.68422 (16)	−0.1763 (13)	0.6532 (3)	0.0204 (12)
C6	0.64889 (16)	−0.0236 (11)	0.6271 (3)	0.0179 (13)
C7	0.61134 (15)	0.3253 (13)	0.5414 (3)	0.0191 (12)
N1	0.61077 (13)	0.4974 (10)	0.4869 (3)	0.0191 (11)
N2	0.57452 (12)	0.6449 (10)	0.4666 (2)	0.0153 (9)
C11	0.57281 (15)	0.8431 (13)	0.4120 (3)	0.0169 (12)
C12	0.53684 (15)	0.9993 (11)	0.3841 (3)	0.0136 (12)
C13	0.53751 (15)	1.2104 (11)	0.3306 (3)	0.0147 (12)
C14	0.57387 (17)	1.2603 (11)	0.3020 (3)	0.0193 (14)
C15	0.61022 (15)	1.1059 (12)	0.3265 (3)	0.0214 (14)
C16	0.60956 (16)	0.9011 (12)	0.3802 (3)	0.0180 (13)
N12	0.49666 (13)	0.9529 (10)	0.4092 (3)	0.0196 (11)
O21	0.49351 (11)	0.7448 (7)	0.4517 (2)	0.0213 (10)
O22	0.46768 (10)	1.1144 (8)	0.38838 (19)	0.0212 (9)
N14	0.57510 (15)	1.4769 (10)	0.2455 (3)	0.0202 (11)
O41	0.54354 (11)	1.6251 (9)	0.2271 (2)	0.0241 (9)
O42	0.60789 (12)	1.5108 (9)	0.2191 (2)	0.0278 (10)
H2	0.6835	0.2845	0.4874	0.030*
H3	0.7437	0.0304	0.5326	0.029*
H5	0.6843	−0.2982	0.6947	0.025*
H6	0.6247	−0.0402	0.6509	0.022*
H7	0.5875	0.3086	0.5660	0.023*
H2A	0.5525	0.6118	0.4888	0.018*
H13	0.5131	1.3185	0.3140	0.018*
H15	0.6352	1.1424	0.3060	0.026*
H16	0.6343	0.7958	0.3965	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.015 (3)	0.021 (3)	0.017 (3)	−0.001 (3)	0.001 (2)	−0.002 (3)
C2	0.025 (3)	0.032 (3)	0.021 (3)	0.000 (3)	0.010 (3)	0.006 (3)
C3	0.017 (3)	0.030 (4)	0.026 (4)	0.003 (3)	0.004 (3)	0.003 (3)
C4	0.020 (3)	0.018 (3)	0.024 (3)	0.004 (3)	0.000 (2)	0.004 (3)
I4	0.0238 (2)	0.0470 (3)	0.0338 (3)	0.0126 (2)	0.00383 (16)	0.0104 (3)
C5	0.025 (3)	0.020 (3)	0.015 (3)	0.000 (3)	−0.002 (2)	0.002 (3)
C6	0.018 (3)	0.020 (3)	0.017 (3)	0.004 (2)	0.005 (2)	0.001 (2)
C7	0.018 (3)	0.017 (3)	0.023 (3)	−0.005 (3)	0.004 (2)	−0.001 (3)
N1	0.020 (2)	0.016 (3)	0.022 (3)	0.004 (2)	0.004 (2)	−0.001 (2)
N2	0.016 (2)	0.016 (2)	0.013 (3)	0.000 (2)	0.0012 (19)	−0.001 (2)
C11	0.021 (3)	0.020 (3)	0.010 (3)	−0.001 (3)	0.003 (2)	−0.001 (3)
C12	0.014 (3)	0.019 (3)	0.009 (3)	−0.001 (2)	0.004 (2)	−0.005 (2)
C13	0.015 (3)	0.019 (3)	0.009 (3)	0.001 (2)	−0.001 (2)	−0.002 (2)
C14	0.025 (3)	0.024 (4)	0.008 (3)	0.000 (2)	0.002 (2)	0.002 (2)
C15	0.012 (3)	0.031 (4)	0.021 (3)	−0.002 (3)	0.005 (2)	−0.003 (3)
C16	0.018 (3)	0.019 (4)	0.018 (3)	−0.001 (2)	0.005 (2)	−0.001 (2)
N12	0.015 (2)	0.027 (3)	0.016 (3)	0.006 (2)	−0.002 (2)	−0.001 (2)
O21	0.021 (2)	0.027 (3)	0.016 (2)	−0.0006 (16)	0.0026 (17)	0.0091 (17)
O22	0.0184 (19)	0.027 (2)	0.017 (2)	0.0037 (19)	0.0007 (16)	0.0011 (18)
N14	0.029 (3)	0.016 (3)	0.015 (3)	0.000 (2)	0.003 (2)	−0.002 (2)
O41	0.026 (2)	0.025 (2)	0.021 (2)	0.002 (2)	−0.0013 (17)	0.0024 (19)
O42	0.028 (2)	0.032 (2)	0.028 (3)	−0.0054 (19)	0.018 (2)	0.0045 (19)

Geometric parameters (Å, º)

C1—C2	1.402 (7)	N2—H2A	0.88
C1—C6	1.402 (7)	C11—C12	1.408 (7)
C1—C7	1.445 (7)	C11—C16	1.419 (7)
C2—C3	1.380 (7)	C12—C13	1.391 (7)
C2—H2	0.95	C12—N12	1.452 (6)
C3—C4	1.405 (8)	C13—C14	1.371 (7)
C3—H3	0.95	C13—H13	0.95
C4—C5	1.368 (7)	C14—C15	1.399 (7)
C4—I4	2.092 (5)	C14—N14	1.449 (7)
C5—C6	1.375 (7)	C15—C16	1.373 (7)
C5—H5	0.95	C15—H15	0.95
C6—H6	0.95	C16—H16	0.95
C7—N1	1.280 (7)	N12—O22	1.221 (5)
C7—H7	0.95	N12—O21	1.254 (5)
N1—N2	1.365 (6)	N14—O42	1.234 (5)
N2—C11	1.357 (7)	N14—O41	1.240 (5)
C2—C1—C6	118.3 (5)	N2—C11—C12	124.6 (5)
C2—C1—C7	121.9 (5)	N2—C11—C16	118.7 (5)
C6—C1—C7	119.8 (5)	C12—C11—C16	116.7 (5)
C3—C2—C1	121.1 (5)	C13—C12—C11	122.0 (5)
C3—C2—H2	119.4	C13—C12—N12	115.4 (4)
C1—C2—H2	119.4	C11—C12—N12	122.7 (5)
C2—C3—C4	118.7 (5)	C14—C13—C12	119.1 (5)
C2—C3—H3	120.7	C14—C13—H13	120.5
C4—C3—H3	120.7	C12—C13—H13	120.5
C5—C4—C3	121.0 (5)	C13—C14—C15	121.2 (5)
C5—C4—I4	120.7 (4)	C13—C14—N14	120.0 (5)
C3—C4—I4	118.2 (4)	C15—C14—N14	118.9 (5)
C4—C5—C6	120.0 (5)	C16—C15—C14	119.5 (5)
C4—C5—H5	120.0	C16—C15—H15	120.3
C6—C5—H5	120.0	C14—C15—H15	120.3
C5—C6—C1	120.8 (5)	C15—C16—C11	121.5 (5)
C5—C6—H6	119.6	C15—C16—H16	119.3
C1—C6—H6	119.6	C11—C16—H16	119.3
N1—C7—C1	120.3 (5)	O22—N12—O21	123.0 (4)
N1—C7—H7	119.8	O22—N12—C12	119.5 (5)
C1—C7—H7	119.8	O21—N12—C12	117.6 (4)
C7—N1—N2	116.6 (4)	O42—N14—O41	122.8 (5)
C11—N2—N1	119.3 (4)	O42—N14—C14	118.5 (5)
C11—N2—H2A	120.4	O41—N14—C14	118.6 (5)
N1—N2—H2A	120.4
C6—C1—C2—C3	−2.4 (9)	C16—C11—C12—N12	177.2 (5)
C7—C1—C2—C3	176.4 (6)	C11—C12—C13—C14	2.6 (8)
C1—C2—C3—C4	0.7 (9)	N12—C12—C13—C14	−177.7 (5)
C2—C3—C4—C5	1.6 (9)	C12—C13—C14—C15	−0.9 (8)
C2—C3—C4—I4	−174.0 (4)	C12—C13—C14—N14	179.3 (5)
C3—C4—C5—C6	−2.2 (9)	C13—C14—C15—C16	−0.2 (8)
I4—C4—C5—C6	173.3 (4)	N14—C14—C15—C16	179.7 (5)
C4—C5—C6—C1	0.4 (8)	C14—C15—C16—C11	−0.4 (8)
C2—C1—C6—C5	1.9 (8)	N2—C11—C16—C15	−177.8 (5)
C7—C1—C6—C5	−177.0 (5)	C12—C11—C16—C15	1.9 (8)
C2—C1—C7—N1	−1.2 (9)	C13—C12—N12—O22	−7.1 (7)
C6—C1—C7—N1	177.7 (5)	C11—C12—N12—O22	172.7 (5)
C1—C7—N1—N2	178.8 (5)	C13—C12—N12—O21	172.7 (4)
C7—N1—N2—C11	176.2 (5)	C11—C12—N12—O21	−7.5 (7)
N1—N2—C11—C12	177.1 (5)	C13—C14—N14—O42	−177.7 (5)
N1—N2—C11—C16	−3.2 (8)	C15—C14—N14—O42	2.4 (7)
N2—C11—C12—C13	176.7 (5)	C13—C14—N14—O41	4.1 (7)
C16—C11—C12—C13	−3.1 (8)	C15—C14—N14—O41	−175.8 (5)
N2—C11—C12—N12	−3.0 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O21	0.88	2.04	2.640 (5)	125
N2—H2A···O21^i	0.88	2.56	3.353 (6)	150
C13—H13···O41^ii	0.95	2.37	3.310 (6)	175

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

(III) 4-Iodobenzaldehyde 4-nitrophenylhydrazone

Crystal data

C13H10IN3O2	F(000) = 712
Mr = 367.14	Dx = 1.742 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 4058 reflections
a = 4.9348 (4) Å	θ = 2.5–32.5°
b = 27.825 (2) Å	µ = 2.29 mm^−1
c = 10.3893 (9) Å	T = 291 K
β = 101.076 (2)°	Plate, orange
V = 1399.99 (19) Å^3	0.42 × 0.20 × 0.04 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	4058 independent reflections
Radiation source: fine-focus sealed X-ray tube	1686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ϕ scans, and ω scans with κ offsets	θmax = 32.5°, θmin = 2.5°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −7→7
Tmin = 0.447, Tmax = 0.914	k = −42→35
7191 measured reflections	l = −15→10

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0438P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.88	(Δ/σ)max < 0.001
4058 reflections	Δρmax = 0.48 e Å^−3
169 parameters	Δρmin = −0.44 e Å^−3
2 restraints	Absolute structure: Flack (1983), 1511 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (3)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.4725 (11)	0.29436 (18)	0.4907 (6)	0.0620 (14)
C4	0.6416 (13)	0.19899 (17)	0.5281 (6)	0.0728 (17)
C2A	0.348 (3)	0.2628 (3)	0.5718 (14)	0.067 (3)*	0.545 (12)
C3A	0.438 (3)	0.2163 (4)	0.5869 (14)	0.073 (3)*	0.545 (12)
C5A	0.770 (3)	0.2314 (4)	0.4489 (13)	0.079 (4)*	0.545 (12)
C6A	0.684 (3)	0.2770 (4)	0.4340 (12)	0.069 (3)*	0.545 (12)
C2B	0.478 (3)	0.2718 (5)	0.6084 (16)	0.062 (4)*	0.455 (12)
C3B	0.561 (3)	0.2239 (4)	0.6350 (15)	0.061 (4)*	0.455 (12)
C5B	0.625 (3)	0.2195 (5)	0.4120 (16)	0.071 (4)*	0.455 (12)
C6B	0.550 (3)	0.2678 (4)	0.3924 (14)	0.059 (4)*	0.455 (12)
I4	0.77441 (15)	0.128099 (11)	0.56208 (11)	0.1064 (2)
C7	0.3867 (12)	0.3444 (2)	0.4713 (6)	0.0688 (15)
N1	0.2262 (11)	0.36303 (13)	0.5428 (7)	0.0643 (16)
N2	0.1661 (9)	0.41057 (16)	0.5248 (5)	0.0668 (13)
C11	0.0103 (10)	0.43269 (17)	0.6021 (6)	0.0548 (12)
C12	−0.1177 (11)	0.40660 (18)	0.6895 (6)	0.0607 (13)
C13	−0.2788 (11)	0.43068 (17)	0.7623 (5)	0.0611 (14)
C14	−0.3117 (10)	0.47934 (17)	0.7529 (5)	0.0521 (12)
C15	−0.1792 (10)	0.50596 (17)	0.6690 (6)	0.0567 (13)
C16	−0.0238 (11)	0.48263 (19)	0.5941 (6)	0.0607 (13)
N14	−0.4857 (9)	0.50331 (17)	0.8303 (5)	0.0649 (13)
O41	−0.6034 (9)	0.47921 (16)	0.9003 (4)	0.0768 (11)
O42	−0.5066 (9)	0.54726 (14)	0.8223 (5)	0.0814 (11)
H2A	0.2092	0.2738	0.6135	0.080*	0.545 (12)
H3A	0.3562	0.1957	0.6390	0.088*	0.545 (12)
H5A	0.9116	0.2206	0.4086	0.095*	0.545 (12)
H6A	0.7698	0.2976	0.3839	0.082*	0.545 (12)
H2B	0.4223	0.2893	0.6750	0.075*	0.455 (12)
H3B	0.5642	0.2096	0.7161	0.073*	0.455 (12)
H5B	0.6645	0.2015	0.3424	0.085*	0.455 (12)
H6B	0.5529	0.2821	0.3117	0.071*	0.455 (12)
H7	0.4472	0.3628	0.4078	0.083*
H2	0.2261	0.4265	0.4651	0.080*
H12	−0.0938	0.3735	0.6979	0.073*
H13	−0.3671	0.4135	0.8191	0.073*
H15	−0.1972	0.5392	0.6645	0.068*
H16	0.0612	0.5001	0.5366	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.071 (3)	0.052 (3)	0.066 (4)	0.004 (3)	0.022 (3)	−0.005 (2)
C4	0.087 (4)	0.049 (3)	0.082 (5)	0.011 (3)	0.015 (3)	−0.002 (3)
I4	0.1229 (3)	0.0594 (2)	0.1328 (4)	0.0207 (3)	0.0147 (3)	−0.0009 (3)
C7	0.080 (4)	0.065 (3)	0.065 (4)	0.010 (3)	0.024 (3)	0.008 (3)
N1	0.064 (4)	0.052 (2)	0.078 (4)	0.006 (2)	0.017 (4)	0.000 (3)
N2	0.071 (3)	0.060 (2)	0.075 (4)	0.009 (2)	0.030 (3)	0.005 (2)
C11	0.051 (3)	0.052 (3)	0.059 (3)	0.003 (2)	0.006 (3)	0.004 (2)
C12	0.068 (3)	0.043 (2)	0.072 (4)	0.004 (2)	0.017 (3)	0.001 (2)
C13	0.064 (3)	0.056 (3)	0.067 (4)	−0.001 (2)	0.022 (3)	0.006 (3)
C14	0.045 (3)	0.054 (3)	0.056 (3)	0.003 (2)	0.007 (2)	−0.004 (2)
C15	0.056 (3)	0.045 (2)	0.068 (4)	0.006 (2)	0.009 (3)	0.004 (2)
C16	0.063 (3)	0.060 (3)	0.062 (4)	0.002 (2)	0.019 (3)	0.008 (3)
N14	0.058 (3)	0.068 (3)	0.063 (3)	0.003 (2)	−0.001 (3)	−0.011 (3)
O41	0.076 (3)	0.079 (3)	0.082 (3)	−0.003 (2)	0.033 (2)	−0.004 (2)
O42	0.096 (3)	0.061 (2)	0.092 (3)	0.013 (2)	0.028 (2)	−0.006 (2)

Geometric parameters (Å, º)

C1—C2B	1.370 (15)	C5B—H5B	0.93
C1—C6B	1.375 (14)	C6B—H6B	0.93
C1—C6A	1.382 (13)	C7—N1	1.294 (9)
C1—C2A	1.434 (13)	C7—H7	0.93
C1—C7	1.457 (7)	N1—N2	1.361 (6)
C4—C5B	1.323 (15)	N2—C11	1.361 (7)
C4—C3A	1.362 (15)	N2—H2	0.86
C4—C3B	1.428 (15)	C11—C16	1.400 (7)
C4—C5A	1.447 (15)	C11—C12	1.404 (8)
C4—I4	2.087 (5)	C12—C13	1.373 (8)
C2A—C3A	1.367 (14)	C12—H12	0.93
C2A—H2A	0.93	C13—C14	1.365 (7)
C3A—H3A	0.93	C13—H13	0.93
C5A—C6A	1.337 (14)	C14—C15	1.398 (8)
C5A—H5A	0.93	C14—N14	1.447 (7)
C6A—H6A	0.93	C15—C16	1.358 (8)
C2B—C3B	1.407 (16)	C15—H15	0.93
C2B—H2B	0.93	C16—H16	0.93
C3B—H3B	0.93	N14—O41	1.216 (6)
C5B—C6B	1.399 (17)	N14—O42	1.229 (5)
C2B—C1—C6B	117.2 (9)	C4—C5B—C6B	121.0 (13)
C2B—C1—C6A	109.5 (8)	C4—C5B—H5B	119.5
C6B—C1—C2A	108.6 (8)	C6B—C5B—H5B	119.5
C6A—C1—C2A	118.7 (7)	C1—C6B—C5B	120.9 (12)
C2B—C1—C7	121.0 (7)	C1—C6B—H6B	119.6
C6B—C1—C7	121.8 (7)	C5B—C6B—H6B	119.6
C6A—C1—C7	119.9 (7)	N1—C7—C1	119.8 (5)
C2A—C1—C7	121.3 (6)	N1—C7—H7	120.1
C5B—C4—C3A	109.6 (9)	C1—C7—H7	120.1
C5B—C4—C3B	121.5 (8)	C7—N1—N2	116.9 (6)
C3A—C4—C5A	118.5 (8)	N1—N2—C11	119.4 (5)
C3B—C4—C5A	110.9 (8)	N1—N2—H2	120.3
C5B—C4—I4	121.5 (7)	C11—N2—H2	120.3
C3A—C4—I4	119.6 (7)	N2—C11—C16	119.3 (5)
C3B—C4—I4	116.9 (6)	N2—C11—C12	121.5 (4)
C5A—C4—I4	121.8 (6)	C16—C11—C12	119.2 (5)
C3A—C2A—C1	118.8 (10)	C13—C12—C11	118.9 (5)
C3A—C2A—H2A	120.6	C13—C12—H12	120.5
C1—C2A—H2A	120.6	C11—C12—H12	120.5
C4—C3A—C2A	122.3 (12)	C14—C13—C12	121.2 (5)
C4—C3A—H3A	118.9	C14—C13—H13	119.4
C2A—C3A—H3A	118.9	C12—C13—H13	119.4
C6A—C5A—C4	119.5 (12)	C13—C14—C15	120.4 (5)
C6A—C5A—H5A	120.3	C13—C14—N14	119.5 (5)
C4—C5A—H5A	120.3	C15—C14—N14	120.0 (5)
C5A—C6A—C1	122.2 (11)	C16—C15—C14	119.1 (5)
C5A—C6A—H6A	118.9	C16—C15—H15	120.4
C1—C6A—H6A	118.9	C14—C15—H15	120.4
C1—C2B—C3B	124.3 (13)	C15—C16—C11	121.0 (5)
C1—C2B—H2B	117.8	C15—C16—H16	119.5
C3B—C2B—H2B	117.8	C11—C16—H16	119.5
C2B—C3B—C4	115.0 (11)	O41—N14—O42	123.1 (5)
C2B—C3B—H3B	122.5	O41—N14—C14	118.7 (5)
C4—C3B—H3B	122.5	O42—N14—C14	118.2 (5)
C2B—C1—C2A—C3A	−81.0 (18)	C5A—C4—C5B—C6B	−75.3 (18)
C6B—C1—C2A—C3A	31.4 (14)	I4—C4—C5B—C6B	−176.6 (10)
C6A—C1—C2A—C3A	−2.0 (16)	C2B—C1—C6B—C5B	1.3 (17)
C7—C1—C2A—C3A	−179.8 (9)	C6A—C1—C6B—C5B	84.9 (18)
C5B—C4—C3A—C2A	−34.9 (16)	C2A—C1—C6B—C5B	−29.7 (15)
C3B—C4—C3A—C2A	84.2 (18)	C7—C1—C6B—C5B	−178.4 (10)
C5A—C4—C3A—C2A	1.0 (17)	C4—C5B—C6B—C1	−5 (2)
I4—C4—C3A—C2A	177.8 (9)	C6B—C1—C7—N1	155.2 (9)
C1—C2A—C3A—C4	0.4 (18)	C6A—C1—C7—N1	−167.3 (8)
C5B—C4—C5A—C6A	82.1 (18)	C2A—C1—C7—N1	10.4 (11)
C3A—C4—C5A—C6A	−0.8 (17)	C2B—C1—C7—N1	−24.5 (11)
C3B—C4—C5A—C6A	−33.7 (15)	C1—C7—N1—N2	176.5 (5)
I4—C4—C5A—C6A	−177.6 (9)	C7—N1—N2—C11	−176.5 (5)
C4—C5A—C6A—C1	−0.9 (19)	N1—N2—C11—C16	172.5 (5)
C2B—C1—C6A—C5A	33.4 (15)	N1—N2—C11—C12	−7.7 (8)
C6B—C1—C6A—C5A	−76.9 (17)	N2—C11—C12—C13	−178.2 (5)
C2A—C1—C6A—C5A	2.3 (16)	C16—C11—C12—C13	1.6 (8)
C7—C1—C6A—C5A	−180.0 (10)	C11—C12—C13—C14	−1.3 (8)
C6B—C1—C2B—C3B	1.1 (18)	C12—C13—C14—C15	−0.5 (8)
C6A—C1—C2B—C3B	−32.9 (16)	C12—C13—C14—N14	179.3 (5)
C2A—C1—C2B—C3B	81.1 (19)	C13—C14—C15—C16	1.9 (8)
C7—C1—C2B—C3B	−179.1 (10)	N14—C14—C15—C16	−177.9 (4)
C1—C2B—C3B—C4	−0.5 (19)	C14—C15—C16—C11	−1.5 (8)
C5B—C4—C3B—C2B	−2.8 (17)	N2—C11—C16—C15	179.6 (5)
C3A—C4—C3B—C2B	−77.7 (17)	C12—C11—C16—C15	−0.3 (8)
C5A—C4—C3B—C2B	33.2 (13)	C13—C14—N14—O41	−1.4 (7)
I4—C4—C3B—C2B	179.0 (9)	C15—C14—N14—O41	178.4 (5)
C3A—C4—C5B—C6B	36.9 (17)	C13—C14—N14—O42	178.3 (5)
C3B—C4—C5B—C6B	5 (2)	C15—C14—N14—O42	−1.9 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O42^i	0.86	2.29	3.117 (7)	163
C16—H16···O41^i	0.93	2.44	3.330 (7)	159

Symmetry code: (i) x+1, −y+1, z−1/2.