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

Nguyen Tien, C.; Le Thi Thu, H.; Nguyen Van, T.; Vu Quoc, T.; Vu Quoc, M.; Pham Chien, T.; Van Meervelt, L.

doi:10.1107/S2056989018008204

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ISSN: 2056-9890

Volume 74| Part 7| July 2018| Pages 910-914

https://doi.org/10.1107/S2056989018008204

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

Cong Nguyen Tien,^a Huong Le Thi Thu,^a Thin Nguyen Van,^b Trung Vu Quoc,^c Manh Vu Quoc,^d Thang Pham Chien ^e and Luc Van Meervelt ^f ^*

^aFaculty of Chemistry, Ho Chi Minh City University of Education, 280 An Duong Vuong Street, District No. 5, Ho Chi Minh City, Vietnam, ^bSchool of Natural Sciences Education, Vinh University, 182 Le Duan St., Vinh City, Vietnam, ^cFaculty of Chemistry, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Vietnam, ^dFaculty of Foundation Science, College of Printing Industry, Phuc Dien, Bac Tu Liem, Hanoi, Vietnam, ^eDepartment of Chemistry, Hanoi University of Science, 19 Le Thanh Tong Street, Hai Ba Trung District, Hanoi, Vietnam, and ^fDepartment of Chemistry, KU Leuven, Biomolecular Architecture, Celestijnenlaan 200F, Leuven (Heverlee), B-3001, Belgium
^*Correspondence e-mail: luc.vanmeervelt@kuleuven.be

Edited by J. Simpson, University of Otago, New Zealand (Received 30 May 2018; accepted 4 June 2018; online 8 June 2018)

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%).

Keywords: crystal structure; N-substituted hydrazide; salicylic acid; Hirshfeld surface.

CCDC reference: 1846971

1. 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.

2. 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).

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) x, y, z-1; (ii) -x+1, -y+1, -z+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.

3. 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 R₂²(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 R₂²(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.

4. 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. 7a) resulted in 461 hits. The histograms of the torsion angles show the distribution for torsion angles tor1 (Fig. 7b) and tor3 (Fig. 7d) as expected for a planar conjugated system. However, the histogram of torsion angle tor2 (Fig. 7c) 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.

5. 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, ⁴J = 2.0, ArH), 7.65 (1H, dd, ³J = 9.0 Hz, ⁴J = 2.0 Hz, ArH), 6.75 (1H, d, ³J = 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 (Csp³—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, ³J = 8.5, ArH), 7.59 (2H, d, ³J = 8.5, ArH), 6.86 (1H, d, ³J = 8.5, ArH), 6.59 (2H, d, ³J = 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.

6. 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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC reference: 1846971

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018008204/sj5557sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018008204/sj5557Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018008204/sj5557Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(E)-N'-[1-(4-Aminophenyl)ethylidene]-2-hydroxy-5-iodobenzohydrazide methanol monosolvate top

Crystal data top

C₁₅H₁₄IN₃O₂·CH₄O	F(000) = 848
M_r = 427.23	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0145P)² + 1.4435P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3394 reflections	Δρ_max = 0.61 e Å⁻³
231 parameters	Δρ_min = −0.24 e Å⁻³
1 restraint

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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) top

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) top

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 information

LVM thanks VLIR–UOS (project ZEIN2014Z182) for financial support.

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