A chain of edge-fused rings generated by the combination of an N-H...O hydrogen bond and an iodo-nitro interaction in 2-iodo­benz­aldehyde 4-nitro­phenyl­hydrazone versus ­disordered and effectively isolated mol­ecules in 2-iodo­benz­aldehyde 2,4-di­nitro­phenyl­hydrazone

Molecules of 2-iodo­benz­aldehyde 4-nitro­phenyl­hydrazone, C₁₃H₁₀IN₃O₂, are effectively planar and are linked by an N-H...O hydrogen bond [H...O = 2.04 Å, N...O = 2.905 (6) Å and N-H...O = 166°] and a two-centre iodo-nitro interaction [I...O = 3.361 (4) Å] into a chain of edge-fused (18) rings. There are no direction-specific interactions between adjacent chains. Molecules of 2-iodo­benz­aldehyde 2,4-di­nitro­phenyl­hydrazone, C₁₃H₉IN₄O₄, are disordered over two orientations with occupancies of 0.681 (5) and 0.319 (5). In the major orientation, there are no direction-specific intermolecular interactions, while for the minor form, a single C-H...O hydrogen bond generates centrosymmetric dimers.

S1. Comment

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 (I) (see scheme) containing a variety of spacer units X, namely arenesulfonamides (Ia) and (Ib) (Kelly et al., 2002), Schiff-base imines (Ic) (Wardell et al., 2002) and (Id) (Glidewell, Howie et al., 2002), and benzylanilines (Ie) (Glidewell, Low et al., 2002). Here we report the structure of two analogous compounds containing the —CH═N—NH— linker unit, 2-iodobenzaldehyde 4-nitrophenylhydrazone (II) and 2-iodobenzaldehyde 2,4-dinitrophenylhydrazone (III), which prove to exhibit radically different patterns of supramolecular aggregation.

Molecules of (II) are essentially planar (Fig. 1), as demonstrated by the torsional angles (Table 1) that define the orientations of the rings relative to the central linked unit, of the nitro group relative to the adjacent ring. The only significant deviation from complete planarity is the 5.9 (3)° twist of the nitro group out of the plane of the aryl ring C11–C16.

The molecules are linked into molecular ladders by the combination of a single N—H···O hydrogen bond (Table 2) and a single two-centre iodo···nitro interaction. Atom I22 in the molecule at (x, y, z) forms an iodo···nitro interaction with atom O42 in the molecule at (x, 2 + y, 1 + z) [I···Oⁱⁱ 3.361 (4) Å, C—I···Oⁱⁱ 146.5 (2)°, I···Oⁱⁱ—Nⁱⁱ 146.9 (3)°; symmetry code ii = (x, 2 + y, 1 + z)], so generating by translation a C(12) chain (Starbuck et al., 1999) running parallel to the [021] direction. At the same time, the amino N1 at (x, y, z) acts as hydrogen-bond donor to O41 at (1.5 − x, 1 + y, 0.5 + z), while N1 at (1.5 − x, 1 + y, 0.5 + z) in turn acts as donor to O41 at (x, 2 + y, 1 + z), so producing a C(8) chain, parallel to [021], generated by the c-glide plane at x = 0.75. The combination of these two motifs generates a molecular ladder (Fig. 2) in which two C(12) iodo···nitro chains act as the uprights while the N—H···O hydrogen bonds act as the rungs. Alternatively, this sub-structure may be described as a chain of edge-fused R³₃(18) rings.

The [021] ladder lies in the domain 0.47 < x < 1.03. Related to this ladder by the action of the 2₁ screw axes is a second chain, running parallel to [0–21] and lying in the domain −0.03 < x < 0.53. There are no direction-specific interactions between adjacent chains. In particular, there are no C—H···O or C—H···π(arene) hydrogen bonds and no aromatic π···π stacking interactions.

Molecules of (III) exhibit orientational disorder (Figs. 3 and 4), with two orientations, having occupancies 0.681 (5) and 0.319 (5), respectively, related to one another approximately via a rotation about the line N1···I22. In both orientations, the molecules are nearly planar, as typified by the torsional angles for the major form (Table 3). In contrast to the supramolecular aggregation in (II), there are neither intermolecular N—H···O hydrogen bonds nor iodo···nitro interactions in (III). In each orientation there is an intramolecular N—H···O hydrogen bond (Table 4), but for most of the intermolecular C—H···O contacts the H···O distances are not significantly shorter than the sum of the van der Waals radii, and so these bonds are not structurally significant. The sole exception occurs for the minor orientation, where centrosymmetrically related molecules are linked into a dimer, via an R²₂(10) motif (Fig. 5). For the major orientation, however, the structure must be regarded as comprising isolated molecules

The occurrence of an iodo···nitro interaction in (II) may be compared with the absence of such an interaction not only in (III) but also in those analogues of types (Ic) and (Id) where the iodo substituent is in a 2-position (Wardell et al., 2002; Glidewell, Howie et al., 2002). Similarly, the absence of aromatic π···π stacking interactions from the structures of (II) and (III) may be compared with the case of 4-nitrobenzylidene-2'-iodoaniline, which is of the type (Id) but has the same disposition of substituents as (II). In 4-nitrobenzylidene-2'-iodoaniline, such interactions link hydrogen-bonded chains into sheets. Clearly, the qualitative prediction of which of the possible weak supramolecular interactions will be significant in compounds of these general types is far from straightforward.

S2. Experimental

For each of (II) and (III), a finely powdered mixture of the aldehyde and the appropriate phenylhydrazine (1:1 molar ratio) was gently heated on a hot-plate until effervescence ceased. The mixtures were cooled and crystallized from ethanol.

S3. Refinement

Compound (II) is orthorhombic and the systematic absences permitted Pca2₁ and Pcam (= Pbcm) as possible space groups. Pca2₁ was chosen and confirmed by the analysis. Compound (III) is triclinic: space group P-1 was selected and confirmed by the structure analysis. In (III), the sites N1 and I22 are common to both orientations. In the minor orientation of (III), the nitrated ring C911–C916 was treated as a rigid hexagon and all non-H atoms in the minor orientation were refined isotropically. DFIX constraints were applied to the nitro group centred on N914. All H atoms were treated as riding atoms with distances C—H = 0.95 Å and N—H = 0.88 Å.

Computing details

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

Figures

	Fig. 1. The molecular structure of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (II) showing the formation of a molecular ladder along [021]. For the sake of clarity, H atoms bonded to C are omitted. The atoms marked with an asterisk (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (1.5 − x, 1 + y, 0.5 + z), (x, 2 + y, 1 + z), (1.5 − x, 3 + y, 1.5 + z) and (1.5 − x, −1 + y, −0.5 + z), respectively.
	Fig. 3. The two molecular orientations in (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. Part of the crystal structure of (III) showing the overlap of the major (full lines) and minor (broken lines) orientations. For the sake of clarity, H atoms are omitted.
	Fig. 5. Part of the crystal structure of (III) showing the centrosymmetric R^22(10) dimer formed by the minor form. The atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 2 − z).

(II) 2-Iodobenzaldehyse-4-nitrophenylhydrazone

Crystal data

C13H10IN3O2	F(000) = 712
Mr = 367.14	Dx = 1.900 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2800 reflections
a = 24.0858 (11) Å	θ = 3.4–27.4°
b = 5.0699 (2) Å	µ = 2.50 mm^−1
c = 10.5080 (4) Å	T = 120 K
V = 1283.16 (9) Å^3	Plate, red
Z = 4	0.32 × 0.08 × 0.06 mm

Data collection

KappaCCD diffractometer	2800 independent reflections
Radiation source: Rotating Anode	2082 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
ϕ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 3.4°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −31→27
Tmin = 0.502, Tmax = 0.865	k = −6→6
8490 measured reflections	l = −13→13

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0298P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.002
2800 reflections	Δρmax = 1.20 e Å^−3
160 parameters	Δρmin = −0.47 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1259 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.08 (4)

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

	x	y	z	Uiso*/Ueq
I22	0.876111 (14)	0.80511 (6)	0.99980 (7)	0.02451 (12)
O41	0.75761 (18)	−0.9173 (10)	0.3440 (4)	0.0298 (10)
O42	0.8286 (2)	−0.7960 (8)	0.2309 (4)	0.0342 (11)
N1	0.8383 (2)	0.0228 (9)	0.6790 (5)	0.0238 (12)
N2	0.88431 (19)	0.1797 (8)	0.6758 (5)	0.0181 (11)
N4	0.7976 (2)	−0.7716 (10)	0.3259 (5)	0.0252 (12)
C11	0.8295 (2)	−0.1731 (11)	0.5902 (5)	0.0169 (13)
C12	0.7819 (3)	−0.3277 (11)	0.6028 (6)	0.0203 (14)
C13	0.7719 (2)	−0.5242 (10)	0.5156 (7)	0.0217 (14)
C14	0.8089 (2)	−0.5666 (12)	0.4170 (5)	0.0190 (12)
C15	0.8567 (2)	−0.4147 (13)	0.4038 (5)	0.0211 (13)
C16	0.8674 (2)	−0.2158 (9)	0.4942 (19)	0.0216 (14)
C21	0.9338 (2)	0.5366 (11)	0.7712 (5)	0.0209 (13)
C22	0.9396 (2)	0.7336 (11)	0.8643 (6)	0.0206 (13)
C23	0.9849 (2)	0.8953 (13)	0.8680 (6)	0.0217 (9)
C24	1.0273 (2)	0.8620 (11)	0.7729 (6)	0.0217 (9)
C25	1.0228 (3)	0.6848 (11)	0.6870 (6)	0.0259 (10)
C26	0.9777 (2)	0.5148 (11)	0.6803 (6)	0.0259 (10)
C27	0.8866 (2)	0.3589 (12)	0.7629 (6)	0.0224 (15)
H1	0.8136	0.0473	0.7395	0.029*
H2	0.8570	0.3748	0.8224	0.027*
H12	0.7567	−0.2975	0.6708	0.024*
H13	0.7396	−0.6307	0.5229	0.026*
H15	0.8816	−0.4445	0.3352	0.025*
H16	0.9003	−0.1126	0.4890	0.026*
H23	0.9883	1.0269	0.9318	0.026*
H24	1.0590	0.9732	0.7740	0.026*
H25	1.0514	0.6689	0.6253	0.031*
H26	0.9761	0.3843	0.6155	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I22	0.02463 (18)	0.02820 (19)	0.02070 (17)	0.00047 (14)	0.0017 (3)	−0.0016 (4)
O41	0.030 (3)	0.027 (2)	0.032 (3)	−0.010 (2)	−0.006 (2)	−0.003 (2)
O42	0.036 (3)	0.045 (3)	0.021 (2)	−0.004 (2)	0.002 (2)	−0.012 (2)
N1	0.026 (3)	0.029 (3)	0.016 (2)	0.000 (2)	0.005 (2)	−0.003 (2)
N2	0.021 (3)	0.014 (3)	0.020 (3)	0.000 (2)	−0.001 (2)	0.003 (2)
N4	0.023 (3)	0.027 (3)	0.025 (3)	0.007 (2)	−0.010 (2)	−0.001 (2)
C11	0.016 (3)	0.017 (3)	0.017 (3)	0.000 (2)	−0.006 (2)	0.006 (3)
C12	0.019 (3)	0.022 (4)	0.019 (3)	0.002 (3)	0.005 (3)	−0.003 (3)
C13	0.017 (3)	0.023 (3)	0.026 (4)	0.0011 (19)	−0.006 (3)	0.004 (4)
C14	0.022 (3)	0.016 (3)	0.018 (3)	0.001 (3)	−0.005 (3)	0.003 (3)
C15	0.022 (3)	0.028 (3)	0.013 (3)	0.005 (3)	0.001 (3)	0.003 (3)
C16	0.016 (3)	0.025 (2)	0.023 (4)	−0.002 (2)	0.008 (5)	0.006 (6)
C21	0.022 (3)	0.018 (3)	0.023 (3)	0.003 (2)	−0.005 (3)	0.003 (3)
C22	0.019 (3)	0.018 (3)	0.024 (3)	0.007 (2)	0.000 (3)	−0.002 (3)
C23	0.013 (2)	0.019 (2)	0.034 (2)	−0.0023 (17)	−0.0059 (18)	0.008 (2)
C24	0.013 (2)	0.019 (2)	0.034 (2)	−0.0023 (17)	−0.0059 (18)	0.008 (2)
C25	0.021 (2)	0.030 (3)	0.027 (2)	0.0056 (17)	0.002 (2)	0.012 (2)
C26	0.021 (2)	0.030 (3)	0.027 (2)	0.0056 (17)	0.002 (2)	0.012 (2)
C27	0.021 (3)	0.023 (3)	0.023 (3)	0.003 (2)	−0.003 (3)	0.002 (3)

Geometric parameters (Å, º)

C11—C16	1.377 (16)	N1—H1	0.88
C11—N1	1.380 (7)	N2—C27	1.291 (8)
C11—C12	1.396 (8)	C27—C21	1.454 (8)
C12—C13	1.375 (8)	C27—H2	0.95
C12—H12	0.95	C21—C22	1.405 (8)
C13—C14	1.384 (8)	C21—C26	1.430 (8)
C13—H13	0.95	C22—C23	1.364 (8)
C14—C15	1.391 (8)	C22—I22	2.121 (6)
C14—N4	1.440 (8)	C23—C24	1.439 (8)
N4—O41	1.229 (7)	C23—H23	0.95
N4—O42	1.252 (7)	C24—C25	1.278 (8)
C15—C16	1.409 (16)	C24—H24	0.95
C15—H15	0.95	C25—C26	1.387 (8)
C16—H16	0.95	C25—H25	0.95
N1—N2	1.364 (6)	C26—H26	0.95
C16—C11—N1	120.4 (6)	C11—N1—H1	119.0
C16—C11—C12	121.7 (6)	C27—N2—N1	115.3 (5)
N1—C11—C12	117.8 (5)	N2—C27—C21	120.8 (5)
C13—C12—C11	119.2 (5)	N2—C27—H2	119.6
C13—C12—H12	120.4	C21—C27—H2	119.6
C11—C12—H12	120.4	C22—C21—C26	116.5 (5)
C12—C13—C14	119.9 (5)	C22—C21—C27	124.0 (5)
C12—C13—H13	120.0	C26—C21—C27	119.4 (5)
C14—C13—H13	120.0	C23—C22—C21	121.7 (6)
C13—C14—C15	121.5 (6)	C23—C22—I22	117.0 (4)
C13—C14—N4	119.2 (5)	C21—C22—I22	121.2 (4)
C15—C14—N4	119.3 (5)	C22—C23—C24	118.5 (5)
O41—N4—O42	122.1 (5)	C22—C23—H23	120.7
O41—N4—C14	118.6 (5)	C24—C23—H23	120.7
O42—N4—C14	119.3 (5)	C25—C24—C23	120.8 (6)
C14—C15—C16	118.7 (7)	C25—C24—H24	119.6
C14—C15—H15	120.7	C23—C24—H24	119.6
C16—C15—H15	120.7	C24—C25—C26	122.6 (6)
C11—C16—C15	119.0 (5)	C24—C25—H25	118.7
C11—C16—H16	120.5	C26—C25—H25	118.7
C15—C16—H16	120.5	C25—C26—C21	119.8 (6)
N2—N1—C11	121.9 (5)	C25—C26—H26	120.1
N2—N1—H1	119.0	C21—C26—H26	120.1
C16—C11—C12—C13	−1.4 (10)	C15—C14—N4—O41	174.6 (5)
N1—C11—C12—C13	179.9 (5)	C13—C14—N4—O42	174.1 (5)
C11—C12—C13—C14	0.1 (8)	C15—C14—N4—O42	−5.6 (8)
C12—C13—C14—C15	0.2 (9)	N2—C27—C21—C26	1.0 (8)
C12—C13—C14—N4	−179.5 (5)	C26—C21—C22—C23	−0.1 (8)
C13—C14—C15—C16	0.7 (10)	C27—C21—C22—C23	179.9 (6)
N4—C14—C15—C16	−179.6 (7)	C26—C21—C22—I22	176.7 (4)
N1—C11—C16—C15	−179.0 (7)	C27—C21—C22—I22	−3.3 (8)
C12—C11—C16—C15	2.3 (13)	C21—C22—C23—C24	0.4 (8)
C14—C15—C16—C11	−1.9 (13)	I22—C22—C23—C24	−176.5 (4)
C16—C11—N1—N2	−0.2 (9)	C22—C23—C24—C25	−0.1 (8)
C11—N1—N2—C27	178.4 (5)	C23—C24—C25—C26	−0.4 (9)
N1—N2—C27—C21	179.1 (5)	C24—C25—C26—C21	0.7 (9)
C12—C11—N1—N2	178.6 (5)	C22—C21—C26—C25	−0.4 (8)
C22—C21—C27—N2	−179.0 (5)	C27—C21—C26—C25	179.6 (5)
C13—C14—N4—O41	−5.8 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O41^i	0.88	2.04	2.905 (6)	166

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

(III) 2-Iodobenzaldehyde 2,4-dinitrophenylhydrazone

Crystal data

C13H9IN4O4	Z = 2
Mr = 412.14	F(000) = 400
Triclinic, P1	Dx = 1.978 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8890 (5) Å	Cell parameters from 2924 reflections
b = 8.1405 (6) Å	θ = 1.7–27.4°
c = 12.176 (1) Å	µ = 2.34 mm^−1
α = 83.876 (4)°	T = 120 K
β = 83.679 (4)°	Plate, orange
γ = 63.151 (3)°	0.08 × 0.06 × 0.01 mm
V = 691.98 (9) Å^3

Data collection

KappaCCD diffractometer	2924 independent reflections
Radiation source: Rotating Anode	2187 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ϕ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 1.7°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −10→9
Tmin = 0.835, Tmax = 0.977	k = −10→10
7346 measured reflections	l = −15→15

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0694P)^2 + 0.0755P] where P = (Fo^2 + 2Fc^2)/3
2924 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.84 e Å^−3
3 restraints	Δρmin = −1.88 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
I22	0.53164 (6)	0.06529 (5)	0.14789 (3)	0.0433 (2)
C11	0.292 (2)	0.375 (2)	0.6377 (12)	0.035 (4)	0.681 (5)
C12	0.1102 (18)	0.4286 (18)	0.6936 (10)	0.023 (2)	0.681 (5)
C13	0.0548 (19)	0.511 (2)	0.7893 (12)	0.033 (3)	0.681 (5)
C14	0.178 (2)	0.547 (2)	0.8405 (10)	0.028 (3)	0.681 (5)
N14	0.121 (3)	0.636 (2)	0.9453 (11)	0.038 (3)	0.681 (5)
O41	−0.0497 (15)	0.700 (2)	0.9755 (14)	0.048 (4)	0.681 (5)
O42	0.2389 (15)	0.6504 (14)	0.9943 (8)	0.064 (3)	0.681 (5)
C15	0.3615 (18)	0.5001 (16)	0.7941 (10)	0.033 (3)	0.681 (5)
C16	0.4195 (17)	0.4165 (16)	0.6933 (9)	0.023 (2)	0.681 (5)
N12	−0.0359 (11)	0.4134 (10)	0.6527 (6)	0.0397 (18)	0.681 (5)
O121	−0.0011 (10)	0.3349 (8)	0.5662 (5)	0.0441 (16)	0.681 (5)
O122	−0.1960 (11)	0.4781 (11)	0.7002 (7)	0.064 (2)	0.681 (5)
C21	0.7318 (13)	0.1108 (11)	0.3385 (7)	0.035 (2)	0.681 (5)
C22	0.7557 (13)	0.0478 (10)	0.2313 (7)	0.036 (2)	0.681 (5)
C23	0.9306 (14)	−0.0210 (12)	0.1744 (8)	0.040 (2)	0.681 (5)
C24	1.086 (3)	−0.033 (2)	0.2216 (14)	0.041 (2)	0.681 (5)
C25	1.0691 (18)	0.0367 (12)	0.3246 (8)	0.041 (2)	0.681 (5)
C26	0.8912 (14)	0.1087 (12)	0.3821 (8)	0.045 (2)	0.681 (5)
C27	0.5497 (14)	0.1763 (10)	0.4046 (8)	0.0410 (15)	0.681 (5)
N2	0.5290 (11)	0.2364 (9)	0.4988 (6)	0.0410 (15)	0.681 (5)
N1	0.3590 (8)	0.2881 (7)	0.5470 (4)	0.0373 (12)
C911	0.322 (3)	0.364 (4)	0.6535 (17)	0.017 (8)*	0.319 (5)
C912	0.456 (2)	0.386 (3)	0.7081 (14)	0.025 (7)*	0.319 (5)
C913	0.403 (2)	0.468 (3)	0.8086 (14)	0.014 (5)*	0.319 (5)
C914	0.217 (3)	0.529 (4)	0.8545 (16)	0.015 (8)*	0.319 (5)
C915	0.084 (2)	0.507 (4)	0.7999 (19)	0.025 (7)*	0.319 (5)
C916	0.136 (3)	0.424 (4)	0.699 (2)	0.034 (9)*	0.319 (5)
N912	0.6091 (18)	0.4068 (16)	0.6531 (10)	0.021 (3)*	0.319 (5)
O921	0.6751 (16)	0.3353 (15)	0.5614 (9)	0.028 (3)*	0.319 (5)
O922	0.6951 (18)	0.4628 (14)	0.7071 (9)	0.024 (3)*	0.319 (5)
N92	0.260 (2)	0.2378 (18)	0.4910 (12)	0.028 (3)*	0.319 (5)
C927	0.338 (2)	0.167 (2)	0.3986 (13)	0.027 (4)*	0.319 (5)
C921	0.235 (2)	0.102 (2)	0.3353 (13)	0.023 (3)*	0.319 (5)
C922	0.307 (3)	0.039 (2)	0.2290 (14)	0.031 (4)*	0.319 (5)
C923	0.214 (2)	−0.036 (2)	0.1712 (13)	0.023 (3)*	0.319 (5)
C924	0.049 (5)	−0.038 (5)	0.215 (3)	0.026 (6)*	0.319 (5)
C925	−0.022 (3)	0.028 (2)	0.3234 (16)	0.023 (4)*	0.319 (5)
C926	0.064 (2)	0.102 (2)	0.3799 (15)	0.024 (3)*	0.319 (5)
N914	0.168 (3)	0.617 (6)	0.956 (2)	0.033 (10)*	0.319 (5)
O941	−0.002 (5)	0.689 (6)	0.990 (4)	0.036 (4)*	0.319 (5)
O942	0.291 (3)	0.616 (3)	1.0139 (16)	0.036 (4)*	0.319 (5)
H13	−0.0708	0.5449	0.8215	0.040*	0.681 (5)
H15	0.4472	0.5247	0.8307	0.040*	0.681 (5)
H16	0.5444	0.3863	0.6610	0.028*	0.681 (5)
H23	0.9444	−0.0603	0.1019	0.048*	0.681 (5)
H24	1.2077	−0.0905	0.1836	0.049*	0.681 (5)
H25	1.1765	0.0349	0.3543	0.049*	0.681 (5)
H26	0.8767	0.1574	0.4519	0.054*	0.681 (5)
H27	0.4441	0.1734	0.3756	0.049*	0.681 (5)
H1	0.2805	0.2614	0.5151	0.045*	0.681 (5)
H91	0.4691	0.2727	0.5131	0.045*	0.319 (5)
H913	0.4945	0.4829	0.8459	0.017*	0.319 (5)
H915	−0.0433	0.5482	0.8313	0.030*	0.319 (5)
H916	0.0448	0.4094	0.6621	0.041*	0.319 (5)
H927	0.4601	0.1566	0.3719	0.032*	0.319 (5)
H923	0.2676	−0.0849	0.1013	0.027*	0.319 (5)
H924	−0.0172	−0.0829	0.1756	0.032*	0.319 (5)
H925	−0.1336	0.0213	0.3566	0.027*	0.319 (5)
H926	0.0087	0.1520	0.4492	0.029*	0.319 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I22	0.0573 (3)	0.0536 (3)	0.0348 (3)	−0.0392 (2)	0.0088 (2)	−0.01212 (19)
C11	0.038 (7)	0.030 (6)	0.034 (6)	−0.014 (5)	−0.015 (6)	0.010 (5)
C12	0.017 (4)	0.020 (4)	0.032 (4)	−0.008 (3)	0.002 (3)	−0.004 (3)
C13	0.025 (4)	0.031 (4)	0.044 (5)	−0.016 (3)	−0.004 (4)	0.009 (3)
C14	0.044 (7)	0.022 (6)	0.016 (5)	−0.015 (5)	0.008 (5)	−0.007 (4)
N14	0.044 (7)	0.026 (6)	0.030 (5)	−0.007 (6)	0.014 (6)	−0.005 (5)
O41	0.045 (8)	0.030 (4)	0.052 (8)	−0.010 (6)	0.031 (7)	−0.003 (5)
O42	0.058 (7)	0.072 (7)	0.044 (5)	−0.004 (5)	−0.029 (5)	−0.021 (4)
C15	0.025 (4)	0.031 (4)	0.044 (5)	−0.016 (3)	−0.004 (4)	0.009 (3)
C16	0.017 (4)	0.020 (4)	0.032 (4)	−0.008 (3)	0.002 (3)	−0.004 (3)
N12	0.040 (5)	0.036 (4)	0.037 (4)	−0.009 (3)	−0.011 (4)	−0.006 (3)
O121	0.060 (4)	0.043 (3)	0.033 (3)	−0.025 (3)	−0.008 (3)	−0.003 (3)
O122	0.033 (4)	0.071 (5)	0.077 (6)	−0.005 (4)	−0.009 (4)	−0.042 (4)
C21	0.041 (5)	0.027 (4)	0.026 (4)	−0.008 (4)	0.004 (4)	0.000 (3)
C22	0.060 (6)	0.020 (4)	0.024 (4)	−0.015 (4)	0.003 (4)	−0.002 (3)
C23	0.050 (6)	0.039 (5)	0.032 (5)	−0.024 (4)	0.009 (4)	0.001 (4)
C24	0.054 (6)	0.031 (4)	0.031 (4)	−0.012 (4)	0.007 (4)	−0.008 (3)
C25	0.054 (6)	0.031 (4)	0.031 (4)	−0.012 (4)	0.007 (4)	−0.008 (3)
C26	0.048 (6)	0.036 (5)	0.035 (5)	−0.006 (4)	0.001 (5)	0.002 (4)
C27	0.047 (4)	0.018 (2)	0.036 (3)	0.002 (2)	0.015 (3)	−0.005 (2)
N2	0.047 (4)	0.018 (2)	0.036 (3)	0.002 (2)	0.015 (3)	−0.005 (2)
N1	0.048 (3)	0.035 (2)	0.026 (2)	−0.015 (2)	0.000 (2)	−0.007 (2)

Geometric parameters (Å, º)

I22—C922	2.019 (17)	C27—H27	0.95
I22—C22	2.077 (10)	N2—N1	1.300 (9)
C11—N1	1.306 (14)	N1—N92	1.309 (15)
C11—C12	1.414 (13)	N1—C911	1.440 (17)
C11—C16	1.441 (18)	N1—H1	0.88
C12—C13	1.339 (13)	N1—H91	0.88
C12—N12	1.364 (14)	C911—C912	1.39
C12—H916	0.7519	C911—C916	1.39
C13—C14	1.358 (18)	C912—N912	1.39 (2)
C13—H13	0.95	C912—C913	1.39
C13—H915	0.8288	C913—C914	1.39
C14—C15	1.389 (15)	C913—H913	0.95
C14—N14	1.460 (12)	C914—C915	1.39
N14—O42	1.214 (17)	C914—N914	1.42 (5)
N14—O41	1.23 (2)	C915—C916	1.39
C15—C16	1.398 (12)	C915—H915	0.95
C15—H15	0.95	C916—H916	0.95
C15—H913	1.2302	N912—O922	1.242 (17)
C16—H16	0.95	N912—O921	1.261 (17)
N12—O122	1.228 (11)	N92—C927	1.28 (2)
N12—O121	1.231 (9)	C927—C921	1.46 (2)
N12—H916	0.6459	C927—H927	0.95
C21—C26	1.410 (14)	C921—C926	1.40 (2)
C21—C22	1.416 (12)	C921—C922	1.41 (2)
C21—C27	1.463 (12)	C922—C923	1.42 (2)
C22—C23	1.368 (13)	C923—C924	1.36 (3)
C23—C24	1.37 (2)	C923—H923	0.95
C23—H23	0.95	C924—C925	1.43 (4)
C24—C25	1.40 (2)	C924—H924	0.95
C24—H24	0.95	C925—C926	1.36 (2)
C25—C26	1.390 (15)	C925—H925	0.95
C25—H25	0.95	C926—H926	0.95
C26—H26	0.95	N914—O941	1.24 (4)
C27—N2	1.261 (12)	N914—O942	1.26 (4)
C922—I22—C22	121.7 (5)	C11—N1—H1	116.6
N1—C11—C12	128.0 (13)	C911—N1—H1	125.4
N1—C11—C16	117.7 (11)	C11—N1—H91	122.0
C12—C11—C16	114.2 (9)	N92—N1—H91	113.9
C13—C12—N12	111.2 (10)	C911—N1—H91	113.9
C13—C12—C11	124.6 (11)	H1—N1—H91	120.7
N12—C12—C11	124.1 (10)	C912—C911—C916	120.0
C12—C13—C14	120.1 (10)	C912—C911—N1	124.5 (13)
C12—C13—H13	119.9	C916—C911—N1	115.5 (13)
C14—C13—H13	119.9	N912—C912—C913	111.3 (12)
C13—C14—C15	120.7 (8)	N912—C912—C911	123.0 (11)
C13—C14—N14	121.0 (13)	C913—C912—C911	120.0
C15—C14—N14	118.3 (15)	C912—C913—C914	120.0
O42—N14—O41	124.1 (12)	C912—C913—H913	120.0
O42—N14—C14	119.4 (15)	C914—C913—H913	120.0
O41—N14—C14	116.4 (15)	C915—C914—C913	120.0
C14—C15—C16	119.6 (10)	C915—C914—N914	121.7 (16)
C14—C15—H15	120.2	C913—C914—N914	118.3 (17)
C16—C15—H15	120.2	C916—C915—C914	120.0
C15—C16—C11	120.8 (9)	C916—C915—H915	120.0
C15—C16—H16	119.6	C914—C915—H915	120.0
C11—C16—H16	119.6	C915—C916—C911	120.0
O122—N12—O121	121.8 (8)	C915—C916—H916	120.0
O122—N12—C12	120.9 (8)	C911—C916—H916	120.0
O121—N12—C12	117.3 (8)	O922—N912—O921	123.2 (13)
C26—C21—C22	118.0 (8)	O922—N912—C912	116.8 (13)
C26—C21—C27	119.6 (8)	O921—N912—C912	118.4 (13)
C22—C21—C27	122.4 (9)	C927—N92—N1	116.5 (13)
C23—C22—C21	120.7 (9)	N92—C927—C921	118.3 (15)
C23—C22—I22	116.1 (6)	N92—C927—H927	120.9
C21—C22—I22	123.2 (7)	C921—C927—H927	120.9
C24—C23—C22	120.2 (10)	C926—C921—C922	119.0 (15)
C24—C23—H23	119.9	C926—C921—C927	120.5 (15)
C22—C23—H23	119.9	C922—C921—C927	120.5 (15)
C23—C24—C25	121.8 (14)	C921—C922—C923	120.4 (15)
C23—C24—H24	119.1	C921—C922—I22	122.5 (12)
C25—C24—H24	119.1	C923—C922—I22	117.0 (12)
C26—C25—C24	118.1 (12)	C924—C923—C922	120.3 (19)
C26—C25—H25	121.0	C924—C923—H923	119.8
C24—C25—H25	121.0	C922—C923—H923	119.8
C25—C26—C21	121.1 (10)	C923—C924—C925	118 (2)
C25—C26—H26	119.4	C923—C924—H924	120.9
C21—C26—H26	119.4	C925—C924—H924	120.9
N2—C27—C21	121.8 (10)	C926—C925—C924	122 (2)
N2—C27—H27	119.1	C926—C925—H925	118.9
C21—C27—H27	119.1	C924—C925—H925	118.9
C27—N2—N1	114.2 (9)	C925—C926—C921	119.6 (18)
N2—N1—C11	126.9 (9)	C925—C926—H926	120.2
N2—N1—N92	109.7 (8)	C921—C926—H926	120.2
C11—N1—N92	123.5 (10)	O941—N914—O942	120 (2)
N2—N1—C911	117.6 (10)	O941—N914—C914	118 (2)
N92—N1—C911	132.1 (11)	O942—N914—C914	122 (2)
N2—N1—H1	116.6
N1—C11—C12—C13	176.9 (14)	N2—N1—C911—C912	0 (2)
C16—C11—C12—C13	0.5 (14)	C11—N1—C911—C912	−149 (11)
N1—C11—C12—N12	−7.7 (18)	N92—N1—C911—C912	170.4 (12)
C16—C11—C12—N12	175.8 (12)	N2—N1—C911—C916	177.3 (10)
N12—C12—C13—C14	−176.9 (12)	C11—N1—C911—C916	29 (9)
C11—C12—C13—C14	−1.1 (14)	N92—N1—C911—C916	−12 (2)
C12—C13—C14—C15	0.6 (15)	C916—C911—C912—N912	−151.0 (19)
C12—C13—C14—N14	−179.7 (15)	N1—C911—C912—N912	26 (2)
C13—C14—N14—O42	173.0 (14)	C916—C911—C912—C913	0.0
C15—C14—N14—O42	−7 (2)	N1—C911—C912—C913	177 (3)
C15—C14—N14—O41	169.5 (15)	N912—C912—C913—C914	154.1 (16)
C13—C14—C15—C16	0.5 (16)	C911—C912—C913—C914	0.0
N14—C14—C15—C16	−179.3 (14)	C912—C913—C914—C915	0.0
C14—C15—C16—C11	−1.0 (17)	C912—C913—C914—N914	−178 (3)
N1—C11—C16—C15	−176.3 (12)	C913—C914—C915—C916	0.0
C12—C11—C16—C15	0.6 (16)	N914—C914—C915—C916	178 (3)
C13—C12—N12—O122	2.9 (13)	C914—C915—C916—C911	0.0
C11—C12—N12—O122	−172.9 (10)	C912—C911—C916—C915	0.0
C13—C12—N12—O121	−178.1 (8)	N1—C911—C916—C915	−177 (2)
C26—C21—C22—C23	3.0 (11)	C913—C912—N912—O922	12 (2)
C27—C21—C22—C23	−176.7 (7)	C911—C912—N912—O922	165.5 (12)
C26—C21—C22—I22	−173.7 (6)	C913—C912—N912—O921	178.5 (13)
C27—C21—C22—I22	6.6 (11)	C911—C912—N912—O921	−28.3 (18)
C922—I22—C22—C23	149.4 (8)	N2—N1—N92—C927	−6.2 (15)
C922—I22—C22—C21	−33.8 (9)	C11—N1—N92—C927	174.3 (13)
C21—C22—C23—C24	1.4 (14)	C911—N1—N92—C927	−177.1 (19)
I22—C22—C23—C24	178.3 (9)	N1—N92—C927—C921	177.7 (12)
C22—C23—C24—C25	−5.2 (18)	N92—C927—C921—C926	−6 (2)
C23—C24—C25—C26	4.3 (18)	N92—C927—C921—C922	174.1 (15)
C24—C25—C26—C21	0.3 (14)	C926—C921—C922—C923	−4 (2)
C22—C21—C26—C25	−3.8 (12)	C927—C921—C922—C923	175.4 (14)
C27—C21—C26—C25	175.9 (8)	C926—C921—C922—I22	171.6 (11)
C26—C21—C27—N2	2.1 (12)	C927—C921—C922—I22	−9 (2)
N1—N2—C27—C21	−179.6 (7)	C22—I22—C922—C921	34.0 (16)
C11—N1—N2—C27	−171.0 (10)	C22—I22—C922—C923	−149.9 (11)
N2—N1—C11—C12	−178.0 (9)	C921—C922—C923—C924	4 (3)
N2—C27—C21—C22	−178.2 (7)	I22—C922—C923—C924	−172.5 (19)
C11—C12—N12—O121	6.1 (14)	C922—C923—C924—C925	−3 (3)
C13—C14—N14—O41	−10 (2)	C923—C924—C925—C926	3 (3)
C27—N2—N1—N92	9.5 (10)	C924—C925—C926—C921	−4 (3)
C27—N2—N1—C911	−178.1 (15)	C922—C921—C926—C925	5 (2)
C16—C11—N1—N2	−1.6 (17)	C927—C921—C926—C925	−175.2 (15)
C12—C11—N1—N92	1.4 (19)	C915—C914—N914—O941	−6 (6)
C16—C11—N1—N92	177.7 (10)	C913—C914—N914—O941	172 (4)
C12—C11—N1—C911	−143 (10)	C915—C914—N914—O942	170 (3)
C16—C11—N1—C911	33 (9)	C913—C914—N914—O942	−12 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O121	0.88	2.06	2.677 (9)	126
N1—H91···O921	0.88	2.07	2.716 (13)	130
C16—H16···O122^i	0.95	2.58	3.301 (18)	133
C23—H23···O41^ii	0.95	2.59	3.438 (18)	149
C913—H913···O942^iii	0.95	2.35	3.21 (3)	150
C916—H916···O922^iv	0.95	2.60	3.34 (3)	136

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