Crystal structure of (E)-N’-[1-(4-amino­phen­yl)ethyl­idene]-2-hy­droxy-5-iodo­benzohydrazide methanol monosolvate

The synthesis and crystal structure of a new N-substituted hydrazide are reported. In the crystal packing, O—H⋯O and N—H⋯O hydrogen bonds predominate together with π–π stacking inter­actions.

Abstract

In the title compound, C₁₅H₁₄IN₃O₂·CH₃OH, two aromatic rings are linked by an N-substituted hydrazide function. The dihedral angle between the aromatic rings is 10.53 (8)°. The stereochemistry about the imine function is E. The methanol mol­ecule forms an O—H⋯O hydrogen bond to the hydrazide O atom. In the crystal, chains of mol­ecules running along the c-axis direction are formed by O—H⋯O hydrogen bonds. Adjacent chains are linked through N—H⋯O hydrogen bonds and π–π stacking inter­actions. The inter­molecular inter­actions in the crystal packing were investigated using Hirshfeld surface analysis, which indicated that the most significant contacts are H⋯H (38.2%), followed by C⋯H/H⋯C (20.6%), O⋯H/H⋯O (11.1%) and I⋯H/H⋯I (9.7%).

Chemical context  

N-substituted hydrazides have been attracted much attention for their structures, coordination ability, biological activities and transformations to heterocyclic compounds (Majumdar et al., 2014 ▸; Asif & Husain, 2013 ▸; Khan et al., 2017 ▸). Derivatives of salicylic acid act as anti­bacterial (Kumar et al., 2012 ▸; Cui et al., 2014 ▸; Sarshira et al., 2016 ▸), anti­fungal (Wodnicka et al., 2017 ▸; Abbas et al., 2017 ▸) and anti­tumor (Murty et al., 2014 ▸) agents. In addition, some salicylhydrazones exhibit significant anti­trypanosomal activity with IC₅₀ ranging from 1 to 34 µM. N-substituted hydrazides containing the typical –C(O)—NH—N=C< functional group can be prepared by a condensation reaction between a hydrazide and a carbonyl compound (an aldehyde or a ketone).

As a continuation of our research work to synthesize derivatives of 5-iodo­salicylohydrazide (Nguyen et al., 2012 ▸), the new compound (E)-N’-[1-(4-amino­phen­yl)ethyl­idene]-2-hy­droxy-5-iodo­benzohydrazide methanol monosolvate was synthesized. The structure of the compound was determined by IR, ¹H NMR, ¹³C NMR and HR–MS spectroscopy as well as X-ray diffraction and the crystal structure is reported herein.

Structural commentary  

The title compound (Fig. 1 ▸) crystallizes as a methanol monosolvate in the monoclinic space group P2₁/c with one hydrazide mol­ecule and a methanol solvate mol­ecule in the asymmetric unit. The OH group of methanol is hydrogen bonded to the hydrazide oxygen atom O4 (Fig. 1 ▸, Table 1 ▸). The dihedral angle between the aromatic rings is 10.53 (8)°. This relatively planar character of the mol­ecule is caused by an intra­molecular hydrogen bond, N2—H2⋯O11 (Table 1 ▸), and the presence of the hydrazide functional group and the C13=N1 double bond. The r.m.s. deviation from a plane through all 21 non-Hatoms is 0.291 Å [with a maximum deviation of 0.838 (1) Å observed for atom O4]. The torsion angles about the bonds of the hydrazide link between the two aromatic rings are: C15—C13=N1—N2 = −175.48 (15)°, C13=N1—N2—C3 = 178.71 (16)° and N1—N2—C3—C5 = −172.18 (15)°. The stereochemistry about the imine function C13=N1 is E. The planar character causes short contacts for the H atoms of methyl group C14 with the H atoms on atoms N2 and C20. As a consequence, this methyl group displays rotational disorder with occupancies of 0.66 (2) and 0.34 (2).

Figure 1.

View of the asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small circles of arbitrary radii. Intra- and inter­molecular hydrogen bonds are shown as dashed lines.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O23—H23⋯O4	0.80 (2)	1.97 (2)	2.7561 (18)	170 (3)
N2—H2⋯O11	0.82 (3)	2.02 (2)	2.665 (2)	134.4 (19)
O11—H11⋯O23i	0.76 (3)	1.88 (3)	2.6323 (18)	172 (2)
N21—H21A⋯O4ii	0.85 (2)	2.14 (2)	2.961 (2)	164 (2)

Symmetry codes: (i) ; (ii) .

Supra­molecular features  

In the crystal, chains of mol­ecules are formed along the c-axis direction by alternating O11—H11⋯O23ⁱ and O23—H23⋯O4 hydrogen bonds (Table 1 ▸ and Fig. 2 ▸). The inter­action of adjacent chains through N21—H21A⋯O4ⁱⁱ hydrogen bonds results in the formation of dimers with graph set (22) (Table 1 ▸ and Fig. 3 ▸). Both aromatic rings are involved in π–π stacking inter­actions [Cg1⋯Cg1ⁱ = 3.9769 (10) Å, slippage 2.042 Å and Cg1⋯Cg2ⁱⁱ = 3.8635 (11) Å, slippage 1.596 Å; Cg1 and Cg2 are the centroids of rings C5–C10 and C15–C20, respectively; Fig. 4 ▸]. The crystal packing contains no voids.

Figure 2.

Part of the crystal packing of the title compound, showing the chain along the c-axis direction formed by O—H⋯O hydrogen-bonding inter­actions [see Table 1 ▸; symmetry code: (i) x, y, z − 1]. Only the major component of the disordered methyl group C14 is shown.

Figure 3.

Ring of graph-set motif (22) formed by N—H⋯O hydrogen-bonding inter­actions [see Table 1 ▸; symmetry code: (i) x − 1, y − 1, z − 2].

Figure 4.

Part of the crystal packing of the title compound, showing the π–π stacking inter­actions between the amino­phenyl (blue) and iodo­phenyl (yellow) rings [symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x, −y + 1, −z + 1].

Additional insight into the crystal packing forces was obtained from a Hirshfeld surface analysis using CrystalExplorer (McKinnon et al., 2007 ▸; Spackman & Jayatilaka, 2009 ▸). The largest bright-red spots on the Hirshfeld surface mapped over d _norm correspond to the (N,O)—H⋯O hydrogen-bonding contacts (Fig. 5 ▸). The pale-red spots are the weaker C⋯H (C18⋯H20), H⋯H (H14F⋯H22B), I⋯H (I12⋯H21B) and I⋯O (I12⋯O23) inter­actions. The most important 2D fingerprint plots, decomposed to highlight particular close contacts of atom pairs and their contribution, are given in Fig. 6 ▸. The relative contributions of the different inter­molecular inter­actions to the Hirshfeld surface area in descending order are: H⋯H (38.2%), C⋯H/H⋯C (20.6%), O⋯H/H⋯O (11.1%), I⋯H/H⋯I (9.7%), N⋯H/H⋯N (7.2%) and C⋯C (5.7%). Contributions from the inter­molecular non- or low-polar inter­actions are much greater than the contributions from the O⋯H contacts. The weak I⋯H inter­actions contribute significantly to the crystal packing.

Figure 5.

Views of the Hirshfeld surface for the title compound mapped over d _norm over the range −0.740 to 1.296 a.u. showing the closest methanol mol­ecules.

Figure 6.

Two-dimensional fingerprint plots delineated into different contact types (a)–(d) for the title compound. Each blue dot represents a 0.01 Å bin of points on the Hirshfeld surface, with coordinates corresponding to distances (Å) from the points to the nearest inter­ior (d _i) and exterior (d _e) nuclei. Increasing intensity of overlapping points is shown by a colour coding from blue to cyan. The grey background contours correspond to the plot integrated for all contact types.

Database survey  

A search of the Cambridge Structural Database (CSD, Version 5.39, last update November 2017; Groom et al., 2016 ▸) for the central N-substituted hydrazide moiety (Fig. 7 ▸ a) resulted in 461 hits. The histograms of the torsion angles show the distribution for torsion angles tor1 (Fig. 7 ▸ b) and tor3 (Fig. 7 ▸ d) as expected for a planar conjugated system. However, the histogram of torsion angle tor2 (Fig. 7 ▸ c) shows the presence of three non-planar entries with torsion angle values of −72.1 (refcode XIJTAN; Buzykin et al., 2012 ▸), −67.9 (refcode NIZTUM; Muniz-Miranda et al., 2008 ▸) and +68.6° (XIJTAN; Buzykin et al., 2012 ▸).

Figure 7.

(a) The N-substituted hydrazide fragment used for a search in the CSD (^a refers to acyclic). (b)–(d) Histograms of torsion angles tor1, tor2 and tor3, respectively.

Synthesis and crystallization  

The reaction scheme used to synthesize the title compound, 5, is shown in Fig. 8 ▸. Methyl salicylate, methyl 2-hy­droxy-5-iodo­benzoate and 2-hy­droxy-5-iodo­benzohydrazide were prepared from salicylic acid according to the method described in our earlier work (Nguyen et al., 2012 ▸).

Figure 8.

Reaction scheme for the title compound.

Methyl salicylate, 2: liquid; b.p. 494-495 K, yield 73%.

Methyl 2-hy­droxy-5-iodo­benzoate (methyl 5-iodo­salicylate), 3: white needles, m.p. 347–348 K, yield 85%; IR (ν, cm⁻¹): 3156, 3080, 2949, 1676, 1604, 527.

2-Hy­droxy-5-iodo­benzohydrazide, 4: white needles, m.p. 451 K, yield 79%; IR (ν, cm⁻¹): 3405, 3322, 1626, 1574, 529; ¹H NMR (δ, ppm): 12.41 (1H, br, OH), 10.12 (1H, br, NH), 8.12 (1H, d, ⁴ J = 2.0, ArH), 7.65 (1H, dd, ³ J = 9.0 Hz, ⁴ J = 2.0 Hz, ArH), 6.75 (1H, d, ³ J = 9.0 Hz, ArH), 4.80 (2H, br, NH₂); ¹³C NMR: 166.1 (CO), 158.9, 141.3, 135.5, 119.9, 117.4, 80.5.

(E)-N’-[1-(4-amino­phen­yl)ethyl­idene]-2-hy­droxy-5-iodo­benzohydrazide, 5: A solution of 2-hy­droxy-5-iodo­benzohydrazide 4 and 4′-amino­aceto­phenone was refluxed for 2 h. The reaction mixture was cooled down to room temperature and the precipitate obtained was filtered off and crystallized from methanol to give 5 as yellow crystals in 78% yield. M.p. 515–516 K. IR (ν, cm⁻¹): 3440, 3298, 3201 (OH, N—H), 2932 (Csp ³—H), 1634, 1577 (C=O, C=N); ¹H NMR (δ, ppm and J, Hz): 11.11 (1H, s, NH), 8.23 (1H, s, ArH), 7.70 (1H, d, ³ J = 8.5, ArH), 7.59 (2H, d, ³ J = 8.5, ArH), 6.86 (1H, d, ³ J = 8.5, ArH), 6.59 (2H, d, ³ J = 8.5, ArH), 5.55 (2H, br, NH₂), 2.22 (3H, s, –CH₃); ¹³C NMR (δ, ppm): 161.1 (C=O), 157.0, 154.8, 150.9, 141.6, 138.7, 128.3, 125.2, 121.0, 120.1, 113.7, 82.0, 14.1; MS: m/z 396.0069 (M+H)⁺, calculated for C₁₅H₁₅IN₃O₂: 396.0209.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms attached to atoms N2, N21, O11 and O23 were found in a difference-Fourier map and refined freely. The other H atoms were placed at calculated positions and refined in riding mode, with C—H distances of 0.95 (aromatic) and 0.98 Å (CH₃), and isotropic displacement parameters equal to 1.2U _eq of the parent atoms (1.5U _eq for CH₃). The difference-Fourier map indicated disorder for the H atoms of methyl group C14. The final occupancy factors for the two sets of H atoms are 0.66 (2) and 0.34 (2). In the final cycles of refinement, two reflections showing very poor agreement were omitted as outliers.

Table 2. Experimental details.

Crystal data
Chemical formula	C15H14IN3O2·CH4O
M r	427.23
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	100
a, b, c (Å)	12.9877 (10), 14.8982 (10), 8.5593 (6)
β (°)	91.806 (2)
V (Å3)	1655.3 (2)
Z	4
Radiation type	Mo Kα
μ (mm−1)	1.95
Crystal size (mm)	0.41 × 0.27 × 0.22
Data collection
Diffractometer	Bruker D8 Quest CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.613, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	45415, 3394, 3086
R int	0.044
(sin θ/λ)max (Å−1)	0.625
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.017, 0.041, 1.06
No. of reflections	3394
No. of parameters	231
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.61, −0.24

Computer programs: APEX2 and SAINT (Bruker, 2013 ▸), SHELXS (Sheldrick, 2008 ▸), SHELXL2016 (Sheldrick, 2015 ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Supplementary Material

CCDC reference: 1846971

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

C15H14IN3O2·CH4O	F(000) = 848
Mr = 427.23	Dx = 1.714 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.9877 (10) Å	Cell parameters from 9842 reflections
b = 14.8982 (10) Å	θ = 3.1–30.5°
c = 8.5593 (6) Å	µ = 1.95 mm−1
β = 91.806 (2)°	T = 100 K
V = 1655.3 (2) Å3	Block, yellow
Z = 4	0.41 × 0.27 × 0.22 mm

Data collection

Bruker D8 Quest CMOS diffractometer	3086 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.044
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 26.4°, θmin = 3.1°
Tmin = 0.613, Tmax = 0.746	h = −16→16
45415 measured reflections	k = −18→18
3394 independent reflections	l = −10→10

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.017	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.041	w = 1/[σ2(Fo2) + (0.0145P)2 + 1.4435P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
3394 reflections	Δρmax = 0.61 e Å−3
231 parameters	Δρmin = −0.24 e Å−3
1 restraint

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.40946 (11)	0.57600 (10)	0.63743 (17)	0.0163 (3)
N2	0.33272 (11)	0.55807 (10)	0.52645 (18)	0.0161 (3)
H2	0.3379 (16)	0.5699 (15)	0.433 (3)	0.023 (6)*
C3	0.24587 (13)	0.51777 (11)	0.5728 (2)	0.0148 (3)
O4	0.22915 (10)	0.50292 (9)	0.71249 (14)	0.0199 (3)
C5	0.17050 (13)	0.48847 (12)	0.4474 (2)	0.0140 (3)
C6	0.16570 (13)	0.52242 (11)	0.2943 (2)	0.0145 (3)
C7	0.08776 (14)	0.49318 (12)	0.1909 (2)	0.0170 (4)
H7	0.081025	0.519641	0.090110	0.020*
C8	0.01991 (14)	0.42619 (12)	0.2326 (2)	0.0172 (4)
H8	−0.031928	0.405794	0.160228	0.021*
C9	0.02861 (13)	0.38912 (12)	0.3817 (2)	0.0150 (3)
C10	0.10096 (13)	0.42151 (12)	0.48894 (19)	0.0147 (3)
H10	0.103575	0.398069	0.592210	0.018*
O11	0.23620 (10)	0.58419 (9)	0.25082 (15)	0.0182 (3)
H11	0.233 (2)	0.5920 (18)	0.163 (3)	0.042 (8)*
I12	−0.06829 (2)	0.28322 (2)	0.44470 (2)	0.01876 (5)
C13	0.49324 (13)	0.61305 (12)	0.5921 (2)	0.0151 (3)
C14	0.51380 (15)	0.64301 (14)	0.4276 (2)	0.0217 (4)
H14A	0.454135	0.628694	0.359179	0.033*	0.66 (2)
H14B	0.574751	0.611872	0.390192	0.033*	0.66 (2)
H14C	0.525871	0.707940	0.426604	0.033*	0.66 (2)
H14D	0.506928	0.591666	0.356473	0.033*	0.34 (2)
H14E	0.583785	0.667320	0.423635	0.033*	0.34 (2)
H14F	0.464045	0.689520	0.395866	0.033*	0.34 (2)
C15	0.57516 (13)	0.62386 (12)	0.7151 (2)	0.0151 (3)
C16	0.56846 (14)	0.57802 (13)	0.8582 (2)	0.0187 (4)
H16	0.510394	0.540934	0.875386	0.022*
C17	0.64415 (14)	0.58565 (12)	0.9740 (2)	0.0183 (4)
H17	0.637198	0.554354	1.069845	0.022*
C18	0.73134 (13)	0.63918 (12)	0.9518 (2)	0.0156 (3)
C19	0.73773 (14)	0.68645 (12)	0.8117 (2)	0.0176 (4)
H19	0.795006	0.724630	0.795497	0.021*
C20	0.66115 (14)	0.67820 (12)	0.6957 (2)	0.0175 (4)
H20	0.667530	0.710410	0.600736	0.021*
N21	0.80719 (13)	0.64660 (12)	1.06816 (19)	0.0195 (3)
H21A	0.8080 (17)	0.6075 (16)	1.140 (3)	0.025 (6)*
H21B	0.8644 (19)	0.6701 (16)	1.040 (3)	0.028 (6)*
C22	0.31350 (17)	0.69396 (14)	0.9344 (3)	0.0285 (5)
H22A	0.294430	0.732318	0.845110	0.043*
H22B	0.380013	0.665329	0.916393	0.043*
H22C	0.318802	0.730503	1.029528	0.043*
O23	0.23658 (11)	0.62647 (9)	0.95224 (15)	0.0213 (3)
H23	0.242 (2)	0.5898 (15)	0.885 (3)	0.040 (8)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0147 (7)	0.0195 (8)	0.0143 (7)	−0.0010 (6)	−0.0037 (6)	−0.0009 (6)
N2	0.0166 (8)	0.0217 (8)	0.0096 (7)	−0.0024 (6)	−0.0033 (6)	0.0005 (6)
C3	0.0170 (9)	0.0125 (8)	0.0147 (8)	0.0020 (7)	−0.0012 (7)	−0.0008 (7)
O4	0.0229 (7)	0.0257 (7)	0.0109 (6)	−0.0068 (5)	−0.0023 (5)	0.0014 (5)
C5	0.0140 (8)	0.0150 (8)	0.0128 (8)	0.0023 (7)	−0.0015 (6)	−0.0025 (7)
C6	0.0163 (8)	0.0131 (8)	0.0142 (8)	0.0010 (7)	0.0009 (7)	−0.0009 (7)
C7	0.0216 (9)	0.0175 (9)	0.0117 (8)	0.0021 (7)	−0.0031 (7)	0.0013 (7)
C8	0.0166 (9)	0.0193 (9)	0.0154 (8)	0.0010 (7)	−0.0048 (7)	−0.0025 (7)
C9	0.0135 (8)	0.0141 (8)	0.0175 (9)	0.0002 (7)	0.0009 (7)	−0.0018 (7)
C10	0.0166 (8)	0.0155 (9)	0.0118 (8)	0.0031 (7)	−0.0001 (7)	0.0004 (7)
O11	0.0225 (7)	0.0215 (7)	0.0104 (6)	−0.0055 (5)	−0.0012 (5)	0.0029 (5)
I12	0.01767 (7)	0.01657 (7)	0.02193 (7)	−0.00289 (4)	−0.00078 (4)	0.00057 (5)
C13	0.0166 (9)	0.0131 (8)	0.0155 (8)	0.0020 (7)	0.0000 (7)	−0.0006 (7)
C14	0.0206 (9)	0.0279 (10)	0.0166 (9)	−0.0017 (8)	−0.0009 (7)	0.0053 (8)
C15	0.0143 (8)	0.0154 (8)	0.0155 (8)	0.0018 (7)	0.0000 (7)	−0.0009 (7)
C16	0.0154 (9)	0.0216 (9)	0.0190 (9)	−0.0051 (7)	0.0002 (7)	0.0021 (7)
C17	0.0180 (9)	0.0210 (9)	0.0160 (8)	−0.0022 (7)	0.0009 (7)	0.0026 (7)
C18	0.0149 (8)	0.0157 (9)	0.0162 (8)	0.0027 (7)	−0.0006 (7)	−0.0050 (7)
C19	0.0150 (9)	0.0169 (9)	0.0210 (9)	−0.0027 (7)	0.0012 (7)	0.0005 (7)
C20	0.0187 (9)	0.0172 (9)	0.0168 (9)	0.0007 (7)	0.0022 (7)	0.0017 (7)
N21	0.0170 (8)	0.0230 (9)	0.0182 (8)	−0.0038 (7)	−0.0019 (6)	0.0006 (7)
C22	0.0291 (11)	0.0251 (10)	0.0318 (11)	−0.0050 (9)	0.0107 (9)	−0.0034 (9)
O23	0.0277 (7)	0.0223 (7)	0.0140 (6)	−0.0043 (6)	0.0014 (5)	−0.0005 (6)

Geometric parameters (Å, º)

N1—N2	1.381 (2)	C14—H14C	0.9800
N1—C13	1.291 (2)	C14—H14D	0.9800
N2—H2	0.82 (2)	C14—H14E	0.9800
N2—C3	1.349 (2)	C14—H14F	0.9800
C3—O4	1.242 (2)	C15—C16	1.407 (2)
C3—C5	1.495 (2)	C15—C20	1.394 (3)
C5—C6	1.404 (2)	C16—H16	0.9500
C5—C10	1.399 (2)	C16—C17	1.379 (3)
C6—C7	1.394 (2)	C17—H17	0.9500
C6—O11	1.359 (2)	C17—C18	1.403 (3)
C7—H7	0.9500	C18—C19	1.396 (3)
C7—C8	1.386 (3)	C18—N21	1.383 (2)
C8—H8	0.9500	C19—H19	0.9500
C8—C9	1.392 (2)	C19—C20	1.388 (3)
C9—C10	1.380 (2)	C20—H20	0.9500
C9—I12	2.0993 (17)	N21—H21A	0.85 (2)
C10—H10	0.9500	N21—H21B	0.86 (2)
O11—H11	0.76 (3)	C22—H22A	0.9800
C13—C14	1.509 (2)	C22—H22B	0.9800
C13—C15	1.482 (2)	C22—H22C	0.9800
C14—H14A	0.9800	C22—O23	1.429 (2)
C14—H14B	0.9800	O23—H23	0.800 (16)
C13—N1—N2	118.21 (15)	C13—C14—H14A	109.5
N1—N2—H2	123.2 (15)	C13—C14—H14B	109.5
C3—N2—N1	118.42 (15)	C13—C14—H14C	109.5
C3—N2—H2	118.4 (15)	C13—C14—H14D	109.5
N2—C3—C5	116.98 (15)	C13—C14—H14E	109.5
O4—C3—N2	122.40 (16)	C13—C14—H14F	109.5
O4—C3—C5	120.59 (16)	C16—C15—C13	120.20 (16)
C6—C5—C3	125.00 (16)	C20—C15—C13	122.59 (16)
C10—C5—C3	116.05 (15)	C20—C15—C16	117.21 (16)
C10—C5—C6	118.94 (16)	C15—C16—H16	119.2
H14Aa—C14—H14B	109.5	C17—C16—C15	121.57 (17)
H14Ba—C14—H14C	109.5	C17—C16—H16	119.2
H14Aa—C14—H14C	109.5	C16—C17—H17	119.7
H14Db—C14—H14E	109.5	C16—C17—C18	120.63 (17)
H14Eb—C14—H14F	109.5	C18—C17—H17	119.7
H14Db—C14—H14F	109.5	C19—C18—C17	118.27 (16)
C7—C6—C5	119.36 (16)	N21—C18—C17	120.49 (17)
O11—C6—C5	119.30 (15)	N21—C18—C19	121.22 (17)
O11—C6—C7	121.33 (16)	C18—C19—H19	119.7
C6—C7—H7	119.4	C20—C19—C18	120.60 (17)
C8—C7—C6	121.12 (16)	C20—C19—H19	119.7
C8—C7—H7	119.4	C15—C20—H20	119.2
C7—C8—H8	120.4	C19—C20—C15	121.68 (17)
C7—C8—C9	119.19 (16)	C19—C20—H20	119.2
C9—C8—H8	120.4	C18—N21—H21A	117.5 (16)
C8—C9—I12	120.11 (13)	C18—N21—H21B	115.7 (15)
C10—C9—C8	120.35 (16)	H21A—N21—H21B	119 (2)
C10—C9—I12	119.54 (13)	H22A—C22—H22B	109.5
C5—C10—H10	119.6	H22A—C22—H22C	109.5
C9—C10—C5	120.78 (16)	H22B—C22—H22C	109.5
C9—C10—H10	119.6	O23—C22—H22A	109.5
C6—O11—H11	111 (2)	O23—C22—H22B	109.5
N1—C13—C14	125.66 (16)	O23—C22—H22C	109.5
N1—C13—C15	115.19 (15)	C22—O23—H23	109.2 (19)
C15—C13—C14	119.13 (15)
N1—N2—C3—O4	5.9 (3)	C8—C9—C10—C5	−3.6 (3)
N1—N2—C3—C5	−172.18 (15)	C10—C5—C6—C7	4.3 (3)
N1—C13—C15—C16	13.9 (2)	C10—C5—C6—O11	−176.74 (15)
N1—C13—C15—C20	−166.49 (17)	O11—C6—C7—C8	175.98 (16)
N2—N1—C13—C14	3.0 (3)	I12—C9—C10—C5	176.29 (13)
N2—N1—C13—C15	−175.48 (15)	C13—N1—N2—C3	178.71 (16)
N2—C3—C5—C6	−20.8 (3)	C13—C15—C16—C17	179.02 (17)
N2—C3—C5—C10	158.64 (16)	C13—C15—C20—C19	−179.11 (17)
C3—C5—C6—C7	−176.25 (16)	C14—C13—C15—C16	−164.75 (17)
C3—C5—C6—O11	2.7 (3)	C14—C13—C15—C20	14.9 (3)
C3—C5—C10—C9	−179.52 (15)	C15—C16—C17—C18	−0.6 (3)
O4—C3—C5—C6	161.03 (17)	C16—C15—C20—C19	0.6 (3)
O4—C3—C5—C10	−19.5 (2)	C16—C17—C18—C19	1.9 (3)
C5—C6—C7—C8	−5.1 (3)	C16—C17—C18—N21	−179.92 (17)
C6—C5—C10—C9	0.0 (3)	C17—C18—C19—C20	−2.0 (3)
C6—C7—C8—C9	1.5 (3)	C18—C19—C20—C15	0.8 (3)
C7—C8—C9—C10	2.9 (3)	C20—C15—C16—C17	−0.6 (3)
C7—C8—C9—I12	−177.01 (13)	N21—C18—C19—C20	179.84 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O23—H23···O4	0.80 (2)	1.97 (2)	2.7561 (18)	170 (3)
N2—H2···O11	0.82 (3)	2.02 (2)	2.665 (2)	134.4 (19)
O11—H11···O23i	0.76 (3)	1.88 (3)	2.6323 (18)	172 (2)
N21—H21A···O4ii	0.85 (2)	2.14 (2)	2.961 (2)	164 (2)

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

Funding Statement

This work was funded by VLIR-UOS grant ZEIN2014Z182 to L. Van Meervelt.