2′-Amino-5′-benzoyl-5-bromo-6′-methyl-2-oxo­spiro­[indoline-3,4′-pyran]-3′-carbo­nitrile

Naghiyev, F.N.; Hökelek, T.; Khrustalev, V.N.; Khalilov, A.N.; Belay, A.N.

doi:10.1107/S2414314625003748

organic compounds

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ISSN: 2414-3146

Volume 10| Part 5| May 2025| x250374

https://doi.org/10.1107/S2414314625003748

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2′-Amino-5′-benzoyl-5-bromo-6′-methyl-2-oxospiro[indoline-3,4′-pyran]-3′-carbonitrile

Farid N. Naghiyev,^a Tuncer Hökelek,^b Victor N. Khrustalev,^c,^d Ali N. Khalilov ^e and Alebel N. Belay ^f ^*

^aDepartment of Chemistry, Baku State University, Z. Khalilov Str. 23, Az 1148 Baku, Azerbaijan, ^bHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, ^cPeoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow 117198, Russian Federation, ^dN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow 119991, Russian Federation, ^e"Composite Materials" Scientific Research Center, Azerbaijan State Economic University (UNEC), Murtuza Mukhtarov Str. 194, Az 1065, Baku, Azerbaijan, and ^fDepartment of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia
^*Correspondence e-mail: alebel.nibret@bdu.edu.et

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 25 March 2025; accepted 24 April 2025; online 2 May 2025)

In the title compound, C₂₁H₁₄BrN₃O₃, the indoline ring system is almost planar, while the pyran ring is in flattened-boat conformation. In the crystal, N—H⋯O and N—H⋯N hydrogen bonds link the molecules, enclosing R²₂(8) and R²₂(12) ring motifs, into (001) sheets.

Keywords: crystal structure; indoline; hydrogen bond.

CCDC reference: 2446481

Structure description

Some spirooxindoles show enhanced receptor-binding capabilities and diverse biological activities (Naghiyev et al., 2019 ). The 2-oxospiro[indoline-3,4′-pyran] core represents an important subclass of spirooxindoles, incorporating both oxindole and pyran moieties, contributing to their broad pharmacological potential. The presence of electron-withdrawing groups, such as cyano (–CN) and halogens (e.g., bromine), play an important role in modulating the electronic properties, lipophilicity and reactivity of these systems (see e.g., Mamedov et al., 2019 ). As part of our ongoing work in this area, we now report the synthesis and structure of the title compound, C₂₁H₁₄BrN₃O₃ (I).

Compound (I) contains an indoline fused ring, a pyran ring and a benzene ring (Fig. 1). In the indoline ring system, the A (N1/C2/C3/C3A/C7A) and B (C3A/C4–C7/C7A) rings are slightly puckered subtending a dihedral angle of 2.44 (7)°. The pyran C (O2/C3/C8–C11) ring is in a flattened-boat conformation with Cremer–Pople puckering parameters Q_T = 0.91 (2) Å, θ = 94 (1)° and φ = 161.4 (14)° (Fig. 2). Atom C3 in (I) is a stereogenic centre: in the arbitrarily chosen asymmetric unit it has an R configuration, but crystal symmetry generates a racemic mixture.

Figure 1
The molecular structure of (I) with 50% probability ellipsoids.

Figure 2
A partial packing diagram of (I) with N—H⋯O and N—H⋯N hydrogen bonds shown as dashed lines. H atoms not involved in these interactions were omitted for clarity.

In the crystal, N—H⋯O and N—H⋯N hydrogen bonds (Table 1) link the molecules, enclosing R₂²(8) and R₂²(12) ring motifs, into (001) sheets (Fig. 2). Neither significant π–π nor C—H⋯π interactions are observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.84 (2)	2.01 (2)	2.839 (2)	171 (3)
N2—H2A⋯O1ⁱⁱ	0.77 (4)	2.17 (4)	2.885 (3)	155 (3)
N2—H2B⋯N3ⁱⁱⁱ	0.84 (3)	2.22 (3)	3.043 (3)	166 (3)
Symmetry codes: (i) ; (ii) ; (iii) .

To visualize the intermolecular interactions in (I), a Hirshfeld surface (HS) analysis (Fig. 3) was carried out using Crystal Explorer 17.5 (Spackman et al., 2021 ). The overall two-dimensional fingerprint plot is shown in Fig. 4a, and those delineated into the different contact types are illustrated in Fig. 4b–n, together with their relative contributions to the Hirshfeld surface. The most important contributions to the surface are H⋯H (33.3%), H⋯O/O⋯H (16.7%) H⋯C/C⋯H (14.2%) H⋯N/N⋯H (13.0%) and H⋯Br/Br⋯H (11.5%) contacts. The other contact types contribute 2.5% or less.

Figure 3
View of the three-dimensional Hirshfeld surface of (I) plotted over d_norm.

Figure 4
The two-dimensional fingerprint plots for (I), showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯C/C⋯H, (e) H⋯N/N⋯H, (f) H⋯Br/Br⋯H, (g) C⋯C, (h) C⋯O/O⋯C, (i) O⋯Br/Br⋯O, (j) C⋯Br/Br⋯C, (k) N⋯Br/Br⋯N, (l) C⋯N/N⋯C, (m) N⋯N and (n) N⋯O/O⋯N interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

Synthesis and crystallization

A mixture of 1.40 g (0.0051 mol) of 2-(5-bromo-2-oxindolin-3- ylidene)malononitrile and 0.85 g (0.0052 mol) of benzoylacetone was dissolved in 30 ml of methyl alcohol with stirring. The reaction mixture was stirred for 10 min and 7 mol% piperazine hydrate was added and stirring was continued. The reaction mixture was kept for 48 h. Crystals were formed as a result of the evaporation of the solvent. These were separated by filtration and recrystallized from a solvent mixture of ethyl alcohol and water (m.p. 275°C, yield 71%). ¹H NMR (300 MHz, DMSO-d₆, p.p.m.): 1.67 (s, 3H, CH₃); 6.74–7.77 (m, 10H, arom. and NH₂); 10.59 (s, 1H, NH). ¹³C NMR (75 MHz, DMSO-d₆, p.p.m.): 20.17 (CH₃), 50.61 (C_quat.), 55.84 (=C_quat.), 111.24 (CH_arom.), 111.87 (C_quat.), 113.89 (CH_arom.), 118.24 (CN), 127.50 (CH_arom.) 128.37 (CH_arom.), 129.31 (CH_arom.), 132.02 (CH_arom.), 133.94 (CH_arom.), 135.61 (C_arom.), 138.74 (C_arom.), 142.07 (C_arom.), 154.92 (C_quat.), 160.44 (C_quat.), 178.52 (C=O), 194.35 (O=C).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₁₄BrN₃O₃
M_r	436.26
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.4809 (2), 10.5655 (2), 12.0412 (3)
α, β, γ (°)	97.593 (2), 104.947 (2), 94.357 (2)
V (Å³)	905.43 (4)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	3.34
Crystal size (mm)	0.19 × 0.15 × 0.13

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix CCD diffractometer
Absorption correction	Multi-scan
T_min, T_max	0.772, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23470, 3833, 3637
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.117, 1.07
No. of reflections	3833
No. of parameters	266
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)	1.25, −0.67
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX publication routines (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2446481

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625003748/hb4511sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625003748/hb4511Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625003748/hb4511Isup3.cml

checkCIF report

Computing details top

2'-Amino-5'-benzoyl-5-bromo-6'-methyl-2-oxospiro[indoline-3,4'-pyran]-3'-carbonitrile top

Crystal data top

C₂₁H₁₄BrN₃O₃	Z = 2
M_r = 436.26	F(000) = 440
Triclinic, P1	D_x = 1.600 Mg m⁻³
a = 7.4809 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.5655 (2) Å	Cell parameters from 15969 reflections
c = 12.0412 (3) Å	θ = 4.2–77.0°
α = 97.593 (2)°	µ = 3.34 mm⁻¹
β = 104.947 (2)°	T = 100 K
γ = 94.357 (2)°	Prism, colourless
V = 905.43 (4) Å³	0.19 × 0.15 × 0.13 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix CCD diffractometer	3637 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.056
φ and ω scans	θ_max = 77.8°, θ_min = 3.9°
Absorption correction: multi-scan	h = −9→9
T_min = 0.772, T_max = 1.000	k = −11→13
23470 measured reflections	l = −15→15
3833 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0797P)² + 0.589P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3833 reflections	Δρ_max = 1.25 e Å⁻³
266 parameters	Δρ_min = −0.67 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.

Refinement. The N-bound hydrogen atoms were located in a difference Fourier map, and their positions and U_iso values were freely refined. The C-bound hydrogen atom positions were calculated geometrically at distances of 0.95 Å (for aromatic CH) and 0.98 Å (for CH₃) and refined using a riding model with the constraint U_iso(H) = 1.2U_eq (C) or 1.5U_eq (methyl C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	−0.16061 (4)	0.19367 (2)	0.39177 (2)	0.03246 (13)
O1	0.5377 (2)	0.33126 (14)	0.99795 (13)	0.0199 (3)
O2	0.4954 (2)	−0.04326 (14)	0.82672 (13)	0.0199 (3)
O3	0.5431 (3)	0.19720 (16)	0.57324 (15)	0.0297 (4)
N1	0.3204 (3)	0.42221 (17)	0.86972 (16)	0.0191 (4)
N2	0.2919 (3)	−0.11430 (18)	0.91685 (17)	0.0216 (4)
N3	0.0061 (3)	0.14095 (18)	0.95428 (18)	0.0264 (4)
C2	0.4187 (3)	0.32603 (19)	0.90471 (18)	0.0179 (4)
C3	0.3504 (3)	0.20421 (19)	0.81000 (17)	0.0180 (4)
C3A	0.2025 (3)	0.25501 (19)	0.72040 (18)	0.0184 (4)
C4	0.0972 (3)	0.1946 (2)	0.61193 (19)	0.0226 (4)
H4	0.105096	0.107259	0.584491	0.027*
C5	−0.0213 (3)	0.2680 (2)	0.54460 (19)	0.0234 (4)
C6	−0.0356 (3)	0.3954 (2)	0.58398 (19)	0.0223 (4)
H6	−0.121526	0.441296	0.536771	0.027*
C7	0.0755 (3)	0.4567 (2)	0.69262 (19)	0.0212 (4)
H7	0.069938	0.544530	0.719706	0.025*
C7A	0.1936 (3)	0.38420 (19)	0.75885 (18)	0.0185 (4)
C8	0.3499 (3)	−0.01640 (19)	0.87053 (18)	0.0189 (4)
C9	0.2749 (3)	0.09743 (19)	0.86361 (18)	0.0187 (4)
C10	0.5006 (3)	0.1573 (2)	0.75533 (18)	0.0196 (4)
C11	0.5590 (3)	0.0417 (2)	0.76235 (18)	0.0198 (4)
C12	0.1265 (3)	0.12001 (19)	0.91351 (18)	0.0203 (4)
C13	0.5570 (3)	0.2399 (2)	0.67443 (19)	0.0211 (4)
C14	0.6205 (3)	0.3790 (2)	0.72057 (19)	0.0209 (4)
C15	0.7485 (3)	0.4173 (2)	0.8292 (2)	0.0223 (4)
H15	0.796058	0.355165	0.875757	0.027*
C16	0.8059 (3)	0.5482 (2)	0.8687 (2)	0.0261 (5)
H16	0.894582	0.575313	0.941940	0.031*
C17	0.7333 (4)	0.6387 (2)	0.8010 (2)	0.0303 (5)
H17	0.770599	0.727597	0.829038	0.036*
C18	0.6066 (4)	0.6001 (2)	0.6925 (2)	0.0310 (5)
H18	0.557758	0.662435	0.646495	0.037*
C19	0.5516 (3)	0.4701 (2)	0.6518 (2)	0.0255 (5)
H19	0.467016	0.443225	0.577082	0.031*
C20	0.6925 (3)	−0.0187 (2)	0.7052 (2)	0.0250 (4)
H20A	0.783428	−0.055909	0.762348	0.038*
H20B	0.757510	0.046499	0.674309	0.038*
H20C	0.624564	−0.086614	0.641448	0.038*
H1	0.351 (4)	0.4971 (19)	0.907 (2)	0.025 (7)*
H2A	0.360 (5)	−0.165 (3)	0.929 (3)	0.025 (7)*
H2B	0.204 (5)	−0.110 (3)	0.949 (3)	0.024 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03811 (18)	0.02869 (18)	0.01956 (16)	0.00059 (11)	−0.00948 (11)	0.00112 (11)
O1	0.0246 (7)	0.0147 (6)	0.0158 (7)	−0.0005 (5)	−0.0021 (6)	0.0022 (5)
O2	0.0242 (7)	0.0134 (7)	0.0194 (7)	0.0008 (5)	0.0011 (6)	0.0036 (5)
O3	0.0422 (10)	0.0234 (8)	0.0209 (8)	−0.0019 (7)	0.0068 (7)	0.0005 (6)
N1	0.0241 (8)	0.0123 (8)	0.0164 (8)	−0.0012 (7)	−0.0005 (7)	0.0000 (6)
N2	0.0258 (9)	0.0146 (9)	0.0221 (9)	0.0017 (7)	0.0012 (8)	0.0056 (7)
N3	0.0296 (10)	0.0190 (9)	0.0302 (10)	0.0010 (7)	0.0074 (8)	0.0048 (7)
C2	0.0218 (9)	0.0132 (9)	0.0164 (9)	−0.0024 (7)	0.0022 (8)	0.0030 (7)
C3	0.0229 (9)	0.0123 (9)	0.0143 (9)	−0.0018 (7)	−0.0018 (8)	0.0014 (7)
C3A	0.0213 (9)	0.0137 (9)	0.0175 (9)	−0.0008 (7)	0.0003 (8)	0.0045 (7)
C4	0.0266 (10)	0.0179 (10)	0.0187 (10)	−0.0010 (8)	−0.0009 (8)	0.0022 (8)
C5	0.0252 (10)	0.0228 (10)	0.0165 (10)	−0.0031 (8)	−0.0025 (8)	0.0023 (8)
C6	0.0229 (10)	0.0221 (10)	0.0207 (10)	0.0031 (8)	0.0013 (8)	0.0082 (8)
C7	0.0251 (10)	0.0152 (9)	0.0213 (10)	0.0014 (8)	0.0027 (8)	0.0037 (8)
C7A	0.0206 (9)	0.0161 (9)	0.0157 (9)	−0.0017 (7)	0.0007 (8)	0.0015 (7)
C8	0.0209 (9)	0.0138 (9)	0.0156 (9)	−0.0028 (7)	−0.0039 (7)	0.0003 (7)
C9	0.0230 (10)	0.0130 (9)	0.0159 (9)	−0.0015 (7)	−0.0012 (8)	0.0019 (7)
C10	0.0226 (9)	0.0158 (9)	0.0159 (9)	−0.0023 (7)	−0.0004 (8)	0.0008 (7)
C11	0.0233 (9)	0.0159 (9)	0.0152 (9)	−0.0037 (7)	−0.0014 (8)	0.0009 (7)
C12	0.0262 (10)	0.0113 (9)	0.0186 (10)	−0.0015 (7)	−0.0020 (8)	0.0031 (7)
C13	0.0232 (10)	0.0195 (10)	0.0178 (10)	0.0001 (8)	0.0012 (8)	0.0028 (8)
C14	0.0235 (10)	0.0186 (10)	0.0204 (10)	−0.0002 (8)	0.0057 (8)	0.0040 (8)
C15	0.0256 (10)	0.0191 (10)	0.0215 (10)	0.0006 (8)	0.0048 (8)	0.0044 (8)
C16	0.0296 (11)	0.0219 (11)	0.0239 (11)	−0.0046 (9)	0.0057 (9)	0.0005 (9)
C17	0.0395 (13)	0.0159 (10)	0.0331 (13)	−0.0026 (9)	0.0088 (11)	0.0009 (9)
C18	0.0409 (13)	0.0207 (11)	0.0307 (12)	0.0036 (10)	0.0063 (11)	0.0087 (9)
C19	0.0295 (11)	0.0230 (11)	0.0233 (11)	0.0021 (9)	0.0050 (9)	0.0064 (9)
C20	0.0279 (11)	0.0190 (10)	0.0257 (11)	0.0013 (8)	0.0039 (9)	0.0023 (8)

Geometric parameters (Å, º) top

Br1—C5	1.896 (2)	C7—C7A	1.380 (3)
O1—C2	1.232 (3)	C7—H7	0.9500
O2—C8	1.359 (3)	C8—C9	1.369 (3)
O2—C11	1.394 (2)	C9—C12	1.413 (3)
O3—C13	1.217 (3)	C10—C11	1.333 (3)
N1—C2	1.348 (3)	C10—C13	1.506 (3)
N1—C7A	1.411 (3)	C11—C20	1.488 (3)
N1—H1	0.839 (18)	C13—C14	1.496 (3)
N2—C8	1.334 (3)	C14—C19	1.394 (3)
N2—H2A	0.77 (4)	C14—C15	1.395 (3)
N2—H2B	0.84 (3)	C15—C16	1.398 (3)
N3—C12	1.154 (3)	C15—H15	0.9500
C2—C3	1.559 (3)	C16—C17	1.389 (4)
C3—C9	1.514 (3)	C16—H16	0.9500
C3—C3A	1.518 (3)	C17—C18	1.390 (4)
C3—C10	1.524 (3)	C17—H17	0.9500
C3A—C4	1.381 (3)	C18—C19	1.389 (3)
C3A—C7A	1.394 (3)	C18—H18	0.9500
C4—C5	1.394 (3)	C19—H19	0.9500
C4—H4	0.9500	C20—H20A	0.9800
C5—C6	1.389 (3)	C20—H20B	0.9800
C6—C7	1.398 (3)	C20—H20C	0.9800
C6—H6	0.9500

C8—O2—C11	119.18 (16)	C8—C9—C12	119.15 (19)
C2—N1—C7A	111.69 (17)	C8—C9—C3	122.83 (19)
C2—N1—H1	120 (2)	C12—C9—C3	117.95 (18)
C7A—N1—H1	127 (2)	C11—C10—C13	120.5 (2)
C8—N2—H2A	115 (2)	C11—C10—C3	123.11 (19)
C8—N2—H2B	121 (2)	C13—C10—C3	115.54 (18)
H2A—N2—H2B	121 (3)	C10—C11—O2	122.49 (19)
O1—C2—N1	125.97 (19)	C10—C11—C20	128.1 (2)
O1—C2—C3	125.24 (18)	O2—C11—C20	109.42 (17)
N1—C2—C3	108.74 (17)	N3—C12—C9	178.7 (2)
C9—C3—C3A	113.82 (17)	O3—C13—C14	120.62 (19)
C9—C3—C10	109.35 (17)	O3—C13—C10	121.6 (2)
C3A—C3—C10	109.87 (17)	C14—C13—C10	117.71 (18)
C9—C3—C2	108.90 (16)	C19—C14—C15	120.4 (2)
C3A—C3—C2	100.89 (16)	C19—C14—C13	118.6 (2)
C10—C3—C2	113.91 (17)	C15—C14—C13	121.00 (19)
C4—C3A—C7A	121.2 (2)	C14—C15—C16	119.3 (2)
C4—C3A—C3	129.27 (19)	C14—C15—H15	120.4
C7A—C3A—C3	109.29 (18)	C16—C15—H15	120.4
C3A—C4—C5	116.8 (2)	C17—C16—C15	120.0 (2)
C3A—C4—H4	121.6	C17—C16—H16	120.0
C5—C4—H4	121.6	C15—C16—H16	120.0
C6—C5—C4	122.2 (2)	C16—C17—C18	120.5 (2)
C6—C5—Br1	118.69 (17)	C16—C17—H17	119.7
C4—C5—Br1	119.03 (17)	C18—C17—H17	119.7
C5—C6—C7	120.4 (2)	C19—C18—C17	119.7 (2)
C5—C6—H6	119.8	C19—C18—H18	120.2
C7—C6—H6	119.8	C17—C18—H18	120.2
C7A—C7—C6	117.2 (2)	C18—C19—C14	120.0 (2)
C7A—C7—H7	121.4	C18—C19—H19	120.0
C6—C7—H7	121.4	C14—C19—H19	120.0
C7—C7A—C3A	122.0 (2)	C11—C20—H20A	109.5
C7—C7A—N1	128.69 (19)	C11—C20—H20B	109.5
C3A—C7A—N1	109.33 (18)	H20A—C20—H20B	109.5
N2—C8—O2	111.49 (19)	C11—C20—H20C	109.5
N2—C8—C9	126.3 (2)	H20A—C20—H20C	109.5
O2—C8—C9	122.24 (19)	H20B—C20—H20C	109.5

C7A—N1—C2—O1	−179.29 (19)	C3A—C3—C9—C8	129.8 (2)
C7A—N1—C2—C3	−1.9 (2)	C10—C3—C9—C8	6.6 (3)
O1—C2—C3—C9	58.0 (3)	C2—C3—C9—C8	−118.5 (2)
N1—C2—C3—C9	−119.44 (19)	C3A—C3—C9—C12	−53.4 (3)
O1—C2—C3—C3A	178.00 (19)	C10—C3—C9—C12	−176.68 (18)
N1—C2—C3—C3A	0.6 (2)	C2—C3—C9—C12	58.3 (2)
O1—C2—C3—C10	−64.4 (3)	C9—C3—C10—C11	−3.7 (3)
N1—C2—C3—C10	118.23 (19)	C3A—C3—C10—C11	−129.3 (2)
C9—C3—C3A—C4	−67.7 (3)	C2—C3—C10—C11	118.4 (2)
C10—C3—C3A—C4	55.3 (3)	C9—C3—C10—C13	166.01 (17)
C2—C3—C3A—C4	175.8 (2)	C3A—C3—C10—C13	40.4 (2)
C9—C3—C3A—C7A	117.36 (19)	C2—C3—C10—C13	−71.9 (2)
C10—C3—C3A—C7A	−119.64 (19)	C13—C10—C11—O2	−173.27 (18)
C2—C3—C3A—C7A	0.9 (2)	C3—C10—C11—O2	−4.1 (3)
C7A—C3A—C4—C5	−1.7 (3)	C13—C10—C11—C20	5.5 (3)
C3—C3A—C4—C5	−176.1 (2)	C3—C10—C11—C20	174.7 (2)
C3A—C4—C5—C6	−0.6 (3)	C8—O2—C11—C10	9.6 (3)
C3A—C4—C5—Br1	176.89 (16)	C8—O2—C11—C20	−169.36 (18)
C4—C5—C6—C7	2.5 (3)	C11—C10—C13—O3	48.6 (3)
Br1—C5—C6—C7	−175.06 (16)	C3—C10—C13—O3	−121.3 (2)
C5—C6—C7—C7A	−1.9 (3)	C11—C10—C13—C14	−134.9 (2)
C6—C7—C7A—C3A	−0.3 (3)	C3—C10—C13—C14	55.1 (3)
C6—C7—C7A—N1	179.3 (2)	O3—C13—C14—C19	42.0 (3)
C4—C3A—C7A—C7	2.2 (3)	C10—C13—C14—C19	−134.5 (2)
C3—C3A—C7A—C7	177.61 (19)	O3—C13—C14—C15	−137.0 (2)
C4—C3A—C7A—N1	−177.50 (19)	C10—C13—C14—C15	46.5 (3)
C3—C3A—C7A—N1	−2.1 (2)	C19—C14—C15—C16	0.4 (3)
C2—N1—C7A—C7	−177.1 (2)	C13—C14—C15—C16	179.3 (2)
C2—N1—C7A—C3A	2.6 (2)	C14—C15—C16—C17	1.1 (3)
C11—O2—C8—N2	172.17 (17)	C15—C16—C17—C18	−1.4 (4)
C11—O2—C8—C9	−6.6 (3)	C16—C17—C18—C19	0.2 (4)
N2—C8—C9—C12	2.9 (3)	C17—C18—C19—C14	1.3 (4)
O2—C8—C9—C12	−178.52 (19)	C15—C14—C19—C18	−1.6 (3)
N2—C8—C9—C3	179.6 (2)	C13—C14—C19—C18	179.4 (2)
O2—C8—C9—C3	−1.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.84 (2)	2.01 (2)	2.839 (2)	171 (3)
N2—H2A···O1ⁱⁱ	0.77 (4)	2.17 (4)	2.885 (3)	155 (3)
N2—H2B···N3ⁱⁱⁱ	0.84 (3)	2.22 (3)	3.043 (3)	166 (3)

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

Acknowledgements

The authors' contributions are as follows. Conceptualizations, ANK and TH; methodology, FNN and ANB; investigation, TH, VNK and FNN; writing (original draft), TH, VNK and ANK; writing (review and editing of the manuscript), TH and FNN; visualization, TH and ANB; funding acquisition, VNK, TH and ANB; resources, TH, VNK and FNN; supervision, FNN and TH.

Funding information

This work was supported by Baku State University and the RUDN University Strategic Academic Leadership Program. TH is also grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

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