Crystal structure and Hirshfeld surface analysis of 4,5-di­bromo-6-methyl-2-phenyl-2,3,3a,4,5,6,7,7a-octa­hydro-3a,6-ep­oxy-1H-isoindol-1-one

Mertsalov, D.F.; Nadirova, M.A.; Chervyakova, L.V.; Grigoriev, M.S.; Shelukho, E.R.; Çelikesir, S.T.; Akkurt, M.; Mlowe, S.

doi:10.1107/S205698902100116X

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ISSN: 2056-9890

Volume 77| Part 3| March 2021| Pages 237-241

https://doi.org/10.1107/S205698902100116X

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Crystal structure and Hirshfeld surface analysis of 4,5-dibromo-6-methyl-2-phenyl-2,3,3a,4,5,6,7,7a-octahydro-3a,6-epoxy-1H-isoindol-1-one

Dmitriy F. Mertsalov,^a Maryana A. Nadirova,^a Lala V. Chervyakova,^a Mikhail S. Grigoriev,^b Evgeniya R. Shelukho,^a Sevim Türktekin Çelikesir,^c Mehmet Akkurt ^c and Sixberth Mlowe ^d ^*

^aDepartment of Organic Chemistry, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., 117198, Moscow, Russian Federation, ^bFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr. 31, bld. 4, Moscow, 119071, Russian Federation, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^dUniversity of Dar es Salaam, Dar es Salaam University College of Education, Department of Chemistry, PO Box 2329, Dar es Salaam, Tanzania
^*Correspondence e-mail: sixberth.mlowe@duce.ac.tz

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 29 January 2021; accepted 1 February 2021; online 9 February 2021)

In the title compound, C₁₅H₁₅Br₂NO₂, two bridged tetrahydrofuran rings adopt envelope conformations with the O atom as the flap. The pyrrolidine ring also adopts an envelope conformation with the spiro C atom as the flap. In the crystal, the molecules are linked into dimers by pairs of C—H⋯O hydrogen bonds, thus generating R²₂(18) rings. The crystal packing is dominated by H⋯H, Br⋯H, H⋯π and Br⋯π interactions. One of the Br atoms is disordered over two sites with occupation ratio of 0.833 (8):0.167 (8).

Keywords: crystal structure; pyrrolidine ring; tetrahydrofuran ring; epoxyisoindole moiety; Hirshfeld surface analysis.

CCDC reference: 2060298

1. Chemical context

The halogenation of oxabicycloheptenes plays an important role in the chemical transformations of bridged heterocycles because of the ability to carry out a complex transformation of the carbon skeleton in one step, which makes it possible to obtain products that are practically inaccessible in other ways from relatively simple starting compounds. The halogenation reaction of oxabicycloheptenes coupled with carbon- or nitrogen-containing rings, with the help of various halogenating agents, proceeds in two possible general directions, depending on the nature of the halogenating agent and the structure of the substrate. Analysis of the literature data does not allow one to reliably predict the direction of the halogenation of oxabicycloheptenes. It can on the one hand be the halogen-initiated Wagner–Meerwein cationic rearrangement (Jung et al., 1985 ; Ciganek et al., 1995 ; Zubkov et al., 2004 , 2018 ; Zaytsev et al., 2020 ), or on the other hand we can observe electrophilic addition of halogens to multiple bonds (Berson et al., 1954 ; Barlow et al., 1971 ; Kobayashi et al., 1976 ; Solov'eva et al., 1984 ). Halogenated organic compounds are of interest because of their photoactivity in the solid state, high solubility in halocarbons, high thermal and oxidative stability, etc., to which non-covalent halogen bonding can contribute (Afkhami et al., 2017 ; Maharramov et al., 2018 ; Mahmoudi et al., 2017 , 2019 ; Shixaliyev et al., 2014 ). In view of its higher directionality, the halogen bond can be better suited than the hydrogen bond for the building of functional materials by non-covalent self-assembly via specific molecular interactions (Gurbanov et al., 2017 , 2018 ; Kopylovich et al., 2011 ; Ma et al., 2017a ,b , 2020 ; Mahmudov et al., 2012 , 2013 , 2019 , 2020 ). In a previous work (Zubkov et al., 2018), the formation of a halogenated Wagner–Meervein rearrangement product under the action of molecular bromine in dry dichloromethane on isoindole 1 was shown. In this study, the effect of [(Me₂NCOMe)₂H]⁺Br₃⁻ (Rodygin et al., 1992 ; Prokop'eva et al., 2008 ) is reported. The different course of the halogenation reaction was shown to be anti-addition on the double bond with the formation of the title compound, 4,5-dibromo-6-methyl-2-phenylhexahydro-3a,6-epoxy-isoindol-1(4H)-one, 2 (Fig. 1).

Figure 1
Synthesis scheme of 4,5-dibromo-6-methyl-2-phenylhexahydro-3a,6-epoxyisoindol-1(4H)-one (2).

2. Structural commentary

In the title compound (Fig. 2), the pyrrolidine ring (N1/C5–C8), tetrahydrofuran rings (O1/C1–C3/C6 and O1/C3–C6) and the six-membered ring (C1–C6) that generate the epoxyisoindole moiety (O1/N1/C1–C8) are puckered (Cremer & Pople, 1975 ). Both tetrahydrofuran rings adopt envelope conformations with puckering parameters of Q(2) = 0.5749 (14) Å, φ(2) = 0.92 (16)° for (O1/C1–C3/C6) and Q(2) = 0.5460 (14) Å, φ(2) = 183.90 (17)° for (O1/C3–C6). The five-membered pyrrolidine ring has an envelope conformation with a maximum deviation from the mean plane of 0.166 (1) Å at C6 [puckering parameters Q(2) = 0.2630 (16) Å, φ(2) = 253.9 (3)°]. The six-membered ring (C1–C6) has a boat conformation [Q_T = 0.9320 (16) Å, θ = 88.92 (10)°, φ = 298.57 (10)°]. The Br2 atom is disordered over two sites with occupation ratio of 0.833 (8):0.167 (8).

Figure 2
The molecular structure of the title compound with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level. The atoms Br2 and Br2A represent the major and minor components of the disorder, respectively.

3. Supramolecular features

The crystal packing of the title compound is consolidated by C—H⋯O hydrogen bonds (Table 1, Fig. 3) and C—H⋯π and C—Br⋯π interactions (Table 1, Fig. 4). In the crystal, pairs of C—H⋯O hydrogen bonds link molecules into dimers with $[R_{2}^{2}]$ (18) ring motifs (Bernstein et al. 1995 ). These dimers are connected by pairs of C—H⋯π interactions and C—Br⋯π interactions [Br1⋯Cg5ⁱⁱⁱ = 3.9246 (8) Å, C1—Br1⋯Cg5ⁱⁱⁱ = 112.92 (5)°; symmetry code: (iii) 1 − x, −y, 1 − z], thus forming layers parallel to the ab plane. Short atomic contacts are listed in Table 2.

Table 1
Hydrogen-bond geometry (Å, °)

Cg5 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O2ⁱ	0.93	2.58	3.223 (2)	127
C5—H5⋯Cg5ⁱⁱ	0.98	2.49	3.4195 (17)	158
Symmetry codes: (i) ; (ii) .

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
H7A⋯H14	2.56	−1 + x, y, z
Br1⋯Br1	3.4852 (3)	−x, −y, 1 − z
H15C⋯H10	2.53	1 − x, −y, 1 − z
H15B⋯H11	2.40	x, y, −1 + z
Br2A⋯H12	3.13	−1 + x, y, −1 + z
H5⋯C14	2.83	1 − x, 1 − y, 1 − z
H13⋯O2	2.58	2 − x, 1 − y, 1 − z

Figure 3
A view of the intermolecular C—H⋯O interactions in the crystal structure of the title compound. Only the major component of the disorder is shown.

Figure 4
A view of the intermolecular C—H⋯π and C—Br⋯π interactions in the crystal structure of the title compound. Only the major component of the disorder is shown.

4. Hirshfeld surface analysis

In order to present the intermolecular interactions in the crystal structure of the title compound in a visual manner, Hirshfeld surfaces (McKinnon et al., 2007 ) and their associated two-dimensional fingerprint plots (Spackman & McKinnon, 2002 ) were generated using CrystalExplorer17 (Turner et al., 2017 ). The Hirshfeld surface plotted over d_norm in the range −0.1151 to 1.1998 a.u. is shown in Fig. 5 while Fig. 6 shows the full two-dimensional fingerprint plot and those delineated into the major contacts: H⋯H (43.0%), Br⋯H/H⋯Br (21.1%), C⋯H/H⋯C (12.4%) and O⋯H/H⋯O (11.9%). The other contacts (Table 3) are negligible with individual contributions of less than 3.5% and a sum of less than 11.5%.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound

Contact	Percentage contribution
H⋯H	43.0
Br⋯H/H⋯Br	21.1
C⋯H/H⋯C	12.4
O⋯H/H⋯O	11.9
Br⋯C/C⋯Br	3.5
Br⋯Br	2.9
Br⋯O/O⋯Br	2.5
Br⋯N/N⋯Br	1.1
C⋯C	0.5
C⋯N/N⋯C	0.5
C⋯O/O⋯C	0.3
N⋯O/O⋯N	0.1
N⋯N	0.1

Figure 5
A view of the three-dimensional Hirshfeld surface for the title compound, plotted over d_norm in the range −0.1151 to 1.1998 a.u.

Figure 6
A view of the two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) Br⋯H/H⋯Br, (d) C⋯H/H⋯C and (e) O⋯H/H⋯O interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

5. Database survey

A search of the Cambridge Crystallographic Database (CSD version 5.40, update of September 2019; Groom et al., 2016 ) yielded six entries closely related to the epoxyisoindole moiety of the title compound, viz.: (3aR,6S,7aR)-7a-bromo-2-methylsulfonyl-1,2,3,6,7,7a-hexahydro-3a,6-epoxyisoindole (CSD refcode ERIVIL; Temel et al., 2011 ), (3aR,6S,7aR)-7a-chloro-2-[(4-nitrophenyl)sulfonyl]-1,2,3,6,7,7a-hexahydro-3a,6-epoxyisoindole (AGONUH; Temel et al., 2013 ), (3aR,6S,7aR)-7a-chloro-6-methyl-2-[(4-nitrophenyl)sulfonyl]-1,2,3,6,7,7a-hexahydro-3a,6-epoxyisoindole (TIJMIK; Demircan et al., 2013 ), (3aR,6S,7aR)-7a-bromo-2-[(4-methylphenyl)sulfonyl]-1,2,3,6,7,7a-hexahydro-3a,6-epoxyisoindole (UPAQEI; Koşar et al., 2011 ), 5-chloro-7-methyl-3-[(4-methylphenyl)sulfonyl]-10-oxa-3-azatricyclo[5.2.1.01,5]dec-8-ene (YAXCIL; Temel et al., 2012 ) and tert-butyl 3a-chloroperhydro-2,6a-epoxyoxireno(e)isoindole-5-carboxylate (MIGTIG; Koşar et al., 2007 ).

In the crystal of ERIVIL, weak intermolecular C—H⋯O hydrogen bonds link the molecules into $[R_{2}^{2}]$ (8) and $[R_{2}^{2}]$ (14) rings, thus forming the chains along the b-axis direction. In the crystal of AGONUH, C—H⋯O hydrogen bonds link the molecules into zigzag chains running along the b-axis direction. In TIJMIK, two types of C—H⋯O hydrogen bonds generate $[R_{2}^{2}]$ (20) and R₄⁴(26) rings, with adjacent rings running parallel to the ac plane. Further C—H⋯O hydrogen bonds form a C(6) chain, linking the molecules in the b-axis direction. In UPAQEI, molecules are linked by C—H⋯O hydrogen bonds. In YAXCIL, C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. In MIGTIG, the molecules are linked only by weak van der Waals interactions.

6. Synthesis and crystallization

The solution of isoindolone 1 (4 mmol) and the brominating agent (4 mmol) in 15 mL of dry chloroform was heated under reflux for 20 h (TLC control, EtOAc–hexane, 1:1). The reaction mixture was poured into H₂O (50 mL) and extracted with CHCl₃ (3 × 20 mL). The combined organic fractions were dried over anhydrous Na₂SO₄, the solvent was evaporated under reduced pressure, and the solid residue was recrystallized from a hexane–AcOEt (1:1) mixture in the form of colourless needles [yield 0.48 g (30%), m.p. > 413 K (decomposition)].

IR (KBr), ν (cm⁻¹): 1700 (N—C=O), 689 (C—Br). ¹H NMR (CDCl₃, 600.2 MHz, 301 K): δ = 7.63 (d, 2H, H2, H6, HAr, J = 7.6), 7.39 (t, 2H, H3, H5, HAr, J = 7.6), 7.19 (t, 1H, H4, HAr, J = 7.6), 4.33 (d, 1H, H4, J = 2.2), 4.24 (t, 1H, H5, J = 2.2), 4.07 (d, 1H, J = 11.8), 4.02 (d, 1H, H3, J = 11.8), 3.00 (dd, 1H, H7a, J = 5.0, J = 9.6), 2.85 (dd, 1H, H7B, J = 9.6, J = 13.1), 2.07 (ddd, 1H, H7A, J = 2.2, J = 5.0, J = 13.1), 1.58 (s, 3H, CH₃). ¹³C NMR (CDCl₃, 150.9 MHz, 301 K): δ = 172.4, 138.7, 129.0 (2C), 125.1, 120.1 (2C), 89.5, 88.0, 60.4, 57.0, 51.1, 51.1, 36.0, 18.1. MS (APCI): m/z = 404 [M + H]⁺ (⁸¹Br), 402 [M + H]⁺ (⁸¹Br, ⁷⁹Br), 400 [M + H]<⁺ (⁷⁹Br).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All the C-bound H atoms were positioned geometrically, with C—H = 0.93 Å (for aromatic H atoms), 0.98 Å (for methine H atoms), 0.97 Å (for methylene H atoms) and 0.96 Å (for methyl H atoms), and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) [1.5U_eq(C) for methyl H atoms]. The Br2 atom attached to the atom C2 is disordered over two sites, with occupancies of 0.833 (8)/0.167 (8). The two components of the disorder (Br2 and Br2A) were refined with restraints so that their bond lengths are comparable. Owing to poor agreement, five reflections, i.e. (126), ( $[\overline{2}]$ 04), ( $[\overline{1}]$ $[\overline{1}]$ 5), (321) and (006), were omitted from the final cycles of refinement.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅Br₂NO₂
M_r	401.10
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	6.8064 (2), 9.5045 (2), 11.9482 (3)
α, β, γ (°)	79.551 (1), 87.820 (1), 77.083 (1)
V (Å³)	740.89 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.47
Crystal size (mm)	0.14 × 0.13 × 0.13

Data collection
Diffractometer	Bruker Kappa APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.184, 0.273
No. of measured, independent and observed [I > 2σ(I)] reflections	19111, 4387, 3575
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.711

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.059, 1.05
No. of reflections	4387
No. of parameters	187
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2060298

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902100116X/yk2144sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902100116X/yk2144Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902100116X/yk2144Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

8,9-Dibromo-7-methyl-3-phenyl-10-oxa-3-azatricyclo[5.2.1.0^1,5]decan-4-one top

Crystal data top

C₁₅H₁₅Br₂NO₂	Z = 2
M_r = 401.10	F(000) = 396
Triclinic, P1	D_x = 1.798 Mg m⁻³
a = 6.8064 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5045 (2) Å	Cell parameters from 9338 reflections
c = 11.9482 (3) Å	θ = 2.6–29.2°
α = 79.551 (1)°	µ = 5.47 mm⁻¹
β = 87.820 (1)°	T = 296 K
γ = 77.083 (1)°	Fragment, colourless
V = 740.89 (3) Å³	0.14 × 0.13 × 0.13 mm

Data collection top

Bruker Kappa APEXII area-detector diffractometer	3575 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.025
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 30.3°, θ_min = 3.8°
T_min = 0.184, T_max = 0.273	h = −8→9
19111 measured reflections	k = −13→13
4387 independent reflections	l = −16→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0265P)² + 0.1676P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.059	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.34 e Å⁻³
4387 reflections	Δρ_min = −0.35 e Å⁻³
187 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0099 (8)

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)
C1	0.2491 (2)	0.23465 (16)	0.29816 (13)	0.0300 (3)
H1	0.162569	0.333375	0.282028	0.036*
C2	0.3412 (2)	0.18494 (19)	0.18835 (14)	0.0358 (3)
H2	0.312544	0.089368	0.184511	0.043*
C3	0.5718 (2)	0.16536 (17)	0.20591 (13)	0.0315 (3)
C4	0.6318 (2)	0.31286 (17)	0.19882 (13)	0.0346 (3)
H4A	0.580003	0.380680	0.130185	0.041*
H4B	0.776935	0.300779	0.202053	0.041*
C5	0.5290 (2)	0.36343 (16)	0.30594 (13)	0.0302 (3)
H5	0.423305	0.452582	0.285765	0.036*
C6	0.4389 (2)	0.23380 (15)	0.36065 (12)	0.0264 (3)
C7	0.4433 (2)	0.23050 (17)	0.48669 (13)	0.0289 (3)
H7A	0.316869	0.284391	0.512777	0.035*
H7B	0.470492	0.130584	0.528351	0.035*
C8	0.6637 (2)	0.37833 (16)	0.39896 (13)	0.0303 (3)
C9	0.6869 (2)	0.29591 (16)	0.60907 (13)	0.0292 (3)
C10	0.5782 (3)	0.24987 (18)	0.70424 (14)	0.0356 (3)
H10	0.456428	0.224227	0.695094	0.043*
C11	0.6499 (3)	0.2420 (2)	0.81232 (15)	0.0449 (4)
H11	0.575891	0.211181	0.875398	0.054*
C12	0.8306 (3)	0.2794 (2)	0.82762 (17)	0.0480 (4)
H12	0.878984	0.273335	0.900469	0.058*
C13	0.9379 (3)	0.3257 (2)	0.73344 (17)	0.0451 (4)
H13	1.059246	0.351480	0.743341	0.054*
C14	0.8691 (2)	0.33463 (18)	0.62468 (15)	0.0374 (4)
H14	0.943622	0.366258	0.562061	0.045*
C15	0.7046 (3)	0.0567 (2)	0.14292 (16)	0.0463 (4)
H15A	0.841396	0.039666	0.168395	0.069*
H15B	0.697046	0.095089	0.062760	0.069*
H15C	0.660246	−0.033910	0.157404	0.069*
N1	0.60928 (18)	0.30218 (13)	0.49983 (11)	0.0289 (3)
O1	0.57998 (14)	0.11085 (10)	0.32711 (8)	0.0280 (2)
O2	0.79438 (19)	0.44882 (13)	0.38590 (11)	0.0435 (3)
Br1	0.10285 (2)	0.09342 (2)	0.38126 (2)	0.03963 (7)
Br2	0.22893 (10)	0.3267 (3)	0.05089 (6)	0.0579 (2)	0.833 (8)
Br2A	0.2336 (6)	0.2821 (8)	0.0560 (3)	0.0579 (2)	0.167 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0257 (7)	0.0304 (7)	0.0335 (8)	−0.0070 (6)	−0.0009 (6)	−0.0037 (6)
C2	0.0354 (8)	0.0430 (9)	0.0299 (8)	−0.0118 (7)	−0.0030 (6)	−0.0043 (7)
C3	0.0308 (7)	0.0367 (8)	0.0263 (7)	−0.0063 (6)	0.0015 (6)	−0.0053 (6)
C4	0.0350 (8)	0.0404 (8)	0.0284 (8)	−0.0137 (7)	0.0021 (6)	0.0000 (6)
C5	0.0295 (7)	0.0273 (7)	0.0326 (8)	−0.0081 (6)	0.0006 (6)	−0.0002 (6)
C6	0.0237 (6)	0.0262 (7)	0.0291 (7)	−0.0060 (5)	0.0020 (5)	−0.0044 (5)
C7	0.0261 (7)	0.0327 (7)	0.0302 (7)	−0.0114 (6)	0.0041 (6)	−0.0067 (6)
C8	0.0300 (7)	0.0270 (7)	0.0344 (8)	−0.0086 (6)	0.0022 (6)	−0.0048 (6)
C9	0.0292 (7)	0.0265 (7)	0.0322 (8)	−0.0048 (6)	−0.0010 (6)	−0.0074 (6)
C10	0.0376 (8)	0.0386 (8)	0.0333 (8)	−0.0148 (7)	0.0013 (7)	−0.0060 (7)
C11	0.0539 (11)	0.0509 (10)	0.0320 (9)	−0.0194 (8)	−0.0006 (8)	−0.0031 (7)
C12	0.0547 (11)	0.0540 (11)	0.0369 (9)	−0.0164 (9)	−0.0127 (8)	−0.0041 (8)
C13	0.0349 (9)	0.0517 (10)	0.0505 (11)	−0.0124 (8)	−0.0104 (8)	−0.0083 (8)
C14	0.0295 (8)	0.0424 (9)	0.0417 (9)	−0.0092 (7)	0.0012 (7)	−0.0096 (7)
C15	0.0462 (10)	0.0526 (10)	0.0394 (10)	−0.0059 (8)	0.0088 (8)	−0.0145 (8)
N1	0.0282 (6)	0.0313 (6)	0.0298 (6)	−0.0116 (5)	0.0019 (5)	−0.0068 (5)
O1	0.0269 (5)	0.0275 (5)	0.0280 (5)	−0.0034 (4)	0.0020 (4)	−0.0040 (4)
O2	0.0445 (7)	0.0450 (7)	0.0462 (7)	−0.0265 (5)	−0.0004 (5)	−0.0003 (5)
Br1	0.03119 (9)	0.04352 (10)	0.04675 (11)	−0.01621 (7)	0.00310 (7)	−0.00536 (7)
Br2	0.05211 (13)	0.0780 (7)	0.03458 (13)	−0.0074 (3)	−0.01400 (9)	0.0075 (2)
Br2A	0.05211 (13)	0.0780 (7)	0.03458 (13)	−0.0074 (3)	−0.01400 (9)	0.0075 (2)

Geometric parameters (Å, º) top

C1—C6	1.514 (2)	C7—H7A	0.9700
C1—C2	1.539 (2)	C7—H7B	0.9700
C1—Br1	1.9538 (15)	C8—O2	1.2175 (18)
C1—H1	0.9800	C8—N1	1.3722 (19)
C2—C3	1.556 (2)	C9—C10	1.390 (2)
C2—Br2A	1.773 (4)	C9—C14	1.398 (2)
C2—Br2	1.982 (2)	C9—N1	1.413 (2)
C2—H2	0.9800	C10—C11	1.381 (2)
C3—O1	1.4455 (18)	C10—H10	0.9300
C3—C15	1.504 (2)	C11—C12	1.381 (3)
C3—C4	1.533 (2)	C11—H11	0.9300
C4—C5	1.537 (2)	C12—C13	1.377 (3)
C4—H4A	0.9700	C12—H12	0.9300
C4—H4B	0.9700	C13—C14	1.380 (3)
C5—C8	1.513 (2)	C13—H13	0.9300
C5—C6	1.529 (2)	C14—H14	0.9300
C5—H5	0.9800	C15—H15A	0.9600
C6—O1	1.4445 (16)	C15—H15B	0.9600
C6—C7	1.502 (2)	C15—H15C	0.9600
C7—N1	1.4699 (19)

C6—C1—C2	100.18 (11)	N1—C7—C6	102.98 (11)
C6—C1—Br1	111.46 (10)	N1—C7—H7A	111.2
C2—C1—Br1	110.81 (10)	C6—C7—H7A	111.2
C6—C1—H1	111.3	N1—C7—H7B	111.2
C2—C1—H1	111.3	C6—C7—H7B	111.2
Br1—C1—H1	111.3	H7A—C7—H7B	109.1
C1—C2—C3	103.47 (12)	O2—C8—N1	126.42 (15)
C1—C2—Br2A	118.5 (2)	O2—C8—C5	125.35 (14)
C3—C2—Br2A	118.35 (18)	N1—C8—C5	108.22 (12)
C1—C2—Br2	111.70 (12)	C10—C9—C14	118.90 (15)
C3—C2—Br2	114.67 (11)	C10—C9—N1	118.84 (14)
C1—C2—H2	108.9	C14—C9—N1	122.25 (14)
C3—C2—H2	108.9	C11—C10—C9	120.38 (16)
Br2—C2—H2	108.9	C11—C10—H10	119.8
O1—C3—C15	110.86 (13)	C9—C10—H10	119.8
O1—C3—C4	101.92 (12)	C12—C11—C10	120.66 (17)
C15—C3—C4	116.12 (14)	C12—C11—H11	119.7
O1—C3—C2	98.23 (11)	C10—C11—H11	119.7
C15—C3—C2	115.34 (14)	C13—C12—C11	119.02 (18)
C4—C3—C2	111.95 (13)	C13—C12—H12	120.5
C3—C4—C5	100.86 (12)	C11—C12—H12	120.5
C3—C4—H4A	111.6	C12—C13—C14	121.36 (17)
C5—C4—H4A	111.6	C12—C13—H13	119.3
C3—C4—H4B	111.6	C14—C13—H13	119.3
C5—C4—H4B	111.6	C13—C14—C9	119.67 (16)
H4A—C4—H4B	109.4	C13—C14—H14	120.2
C8—C5—C6	102.91 (12)	C9—C14—H14	120.2
C8—C5—C4	117.40 (13)	C3—C15—H15A	109.5
C6—C5—C4	102.89 (12)	C3—C15—H15B	109.5
C8—C5—H5	111.0	H15A—C15—H15B	109.5
C6—C5—H5	111.0	C3—C15—H15C	109.5
C4—C5—H5	111.0	H15A—C15—H15C	109.5
O1—C6—C7	112.07 (12)	H15B—C15—H15C	109.5
O1—C6—C1	102.18 (11)	C8—N1—C9	126.80 (13)
C7—C6—C1	122.52 (12)	C8—N1—C7	112.86 (12)
O1—C6—C5	102.27 (11)	C9—N1—C7	120.22 (12)
C7—C6—C5	105.82 (12)	C6—O1—C3	97.27 (10)
C1—C6—C5	110.27 (12)

C6—C1—C2—C3	−0.64 (15)	O1—C6—C7—N1	85.18 (13)
Br1—C1—C2—C3	−118.41 (11)	C1—C6—C7—N1	−152.93 (13)
C6—C1—C2—Br2A	−133.9 (3)	C5—C6—C7—N1	−25.51 (14)
Br1—C1—C2—Br2A	108.3 (3)	C6—C5—C8—O2	164.98 (15)
C6—C1—C2—Br2	−124.51 (12)	C4—C5—C8—O2	52.9 (2)
Br1—C1—C2—Br2	117.72 (11)	C6—C5—C8—N1	−16.51 (15)
C1—C2—C3—O1	35.54 (14)	C4—C5—C8—N1	−128.64 (14)
Br2A—C2—C3—O1	168.9 (3)	C14—C9—C10—C11	−0.3 (2)
Br2—C2—C3—O1	157.45 (12)	N1—C9—C10—C11	179.79 (15)
C1—C2—C3—C15	153.36 (14)	C9—C10—C11—C12	−0.1 (3)
Br2A—C2—C3—C15	−73.3 (3)	C10—C11—C12—C13	0.4 (3)
Br2—C2—C3—C15	−84.74 (17)	C11—C12—C13—C14	−0.3 (3)
C1—C2—C3—C4	−70.91 (15)	C12—C13—C14—C9	−0.1 (3)
Br2A—C2—C3—C4	62.4 (3)	C10—C9—C14—C13	0.4 (2)
Br2—C2—C3—C4	50.99 (17)	N1—C9—C14—C13	−179.71 (15)
O1—C3—C4—C5	−36.84 (14)	O2—C8—N1—C9	3.2 (3)
C15—C3—C4—C5	−157.42 (14)	C5—C8—N1—C9	−175.27 (13)
C2—C3—C4—C5	67.22 (15)	O2—C8—N1—C7	179.05 (15)
C3—C4—C5—C8	115.57 (14)	C5—C8—N1—C7	0.57 (17)
C3—C4—C5—C6	3.44 (14)	C10—C9—N1—C8	161.81 (15)
C2—C1—C6—O1	−34.97 (13)	C14—C9—N1—C8	−18.1 (2)
Br1—C1—C6—O1	82.31 (11)	C10—C9—N1—C7	−13.8 (2)
C2—C1—C6—C7	−161.36 (13)	C14—C9—N1—C7	166.34 (14)
Br1—C1—C6—C7	−44.08 (16)	C6—C7—N1—C8	15.92 (16)
C2—C1—C6—C5	73.18 (14)	C6—C7—N1—C9	−167.93 (12)
Br1—C1—C6—C5	−169.54 (10)	C7—C6—O1—C3	−167.25 (12)
C8—C5—C6—O1	−91.53 (13)	C1—C6—O1—C3	59.84 (12)
C4—C5—C6—O1	30.94 (14)	C5—C6—O1—C3	−54.35 (13)
C8—C5—C6—C7	25.94 (15)	C15—C3—O1—C6	−178.76 (13)
C4—C5—C6—C7	148.41 (12)	C4—C3—O1—C6	57.05 (12)
C8—C5—C6—C1	160.39 (12)	C2—C3—O1—C6	−57.57 (12)
C4—C5—C6—C1	−77.14 (14)

Hydrogen-bond geometry (Å, º) top

Cg5 is the centroid of the C9–C14 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···Br2	0.97	2.79	3.2838 (17)	113
C13—H13···O2ⁱ	0.93	2.58	3.223 (2)	127
C14—H14···O2	0.93	2.30	2.884 (2)	120
C5—H5···Cg5ⁱⁱ	0.98	2.49	3.4195 (17)	158

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

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
H7A···H14	2.56	-1 + x, y, z
Br1···Br1	3.4852 (3)	-x, -y, 1 - z
H15C···H10	2.53	1 - x, -y, 1 - z
H15B···H11	2.40	x, y, -1 + z
Br2A···H12	3.13	-1 + x, y, -1 + z
H5···C14	2.83	1 - x, 1 - y, 1 - z
H13···O2	2.58	2 - x, 1 - y, 1 - z

Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound top

Contact	Percentage contribution
H···H	43.0
Br···H/H···Br	21.1
C···H/H···C	12.4
O···H/H···O	11.9
Br···C/C···Br	3.5
Br···Br	2.9
Br···O/O···Br	2.5
Br···N/N···Br	1.1
C···C	0.5
C···N/N···C	0.5
C···O/O···C	0.3
N···O/O···N	0.1
N···N	0.1

Funding information

The authors are grateful to the Russian Foundation for Basic Research (RFBR) (award No. 19–53-04002, Bl_ml_a) and the Belarusian Republican Foundation for Fundamental Research (BRFFR) (award No. X19PM-003) for financial support of this research.

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