Crystal structure and Hirshfeld surface analysis of supra­molecular aggregate of 2,2,6,6-tetra­methyl­piperidin-1-ium bromide with 1,2,3,4-tetra­fluoro-5,6-di­iodo­benzene

Gurbanov, A.V.; Hökelek, T.; Mammadova, G.Z.; Hasanov, K.I.; Javadzade, T.A.; Belay, A.N.

doi:10.1107/S2056989024011502

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Volume 81| Part 1| January 2025| Pages 53-57

https://doi.org/10.1107/S2056989024011502

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Crystal structure and Hirshfeld surface analysis of supramolecular aggregate of 2,2,6,6-tetramethylpiperidin-1-ium bromide with 1,2,3,4-tetrafluoro-5,6-diiodobenzene

Atash V. Gurbanov,^a,^b,^c Tuncer Hökelek,^d Gunay Z. Mammadova,^e Khudayar I. Hasanov,^f,^g Tahir A. Javadzade ^h and Alebel N. Belay ⁱ ^*

^aExcellence Center, Baku State University, Z. Xalilov Str. 23, AZ 1148 Baku, Azerbaijan, ^bScientific Research Center, Baku Engineering University, Hasan Aliyev Str. 120, Baku, Absheron AZ0101, Azerbaijan, ^cCentro de Quimica Estrutural, Instituto Superior Tecnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal, ^dHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, ^eDepartment of Chemistry, Baku State University, Z. Khalilov Str. 23, Az 1148 Baku, Azerbaijan, ^fWestern Caspian University, Istiglaliyyat Str. 31, AZ 1001 Baku, Azerbaijan, ^gAzerbaijan Medical University, Scientific Research Centre (SRC), A. Kasumzade Str. 14, AZ 1022 Baku, Azerbaijan, ^hDepartment of Chemistry and Chemical Engineering, Khazar University, Mahzati Str. 41, AZ 1096 Baku, Azerbaijan, and ⁱDepartment of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia
^*Correspondence e-mail: alebel.nibret@bdu.edu.et

Edited by C. Schulzke, Universität Greifswald, Germany (Received 29 October 2024; accepted 26 November 2024; online 1 January 2025)

The asymmetric unit of the title compound, C₉H₂₀N⁺·Br⁻·C₆F₄I₂, contains one 2,2,6,6 tetramethylpiperidine-1-ium cation, one 1,2,3,4-tetrafluoro-5,6-diiodobenzene molecule, and one uncoordinated bromide anion. In the crystal, the bromide anions link the 2,2,6,6-tetramethylpiperidine molecules by intermolecular C—H⋯Br and N—H⋯Br hydrogen bonds, leading to dimers, with the coplanar 1,2,3,4-tetrafluoro-5,6-diiodobenzene molecules filling the space between them. There is a π–π interaction between the almost parallel benzene rings [dihedral angle = 10.5 (2)°] with a centroid-to-centroid distance of 3.838 (3) Å and slippage of 1.468 Å. No C—H⋯π(ring) interactions are observed. A Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯F/F⋯H (23.8%), H⋯H (22.6%), H⋯Br/Br⋯H (17.3%) and H⋯I/I⋯H (13.8%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing.

Keywords: crystal structure; non-covalent interactions; halogen bond.

CCDC reference: 2405482

1. Chemical context

The halogen bond (HaB) is defined as a non-covalent interaction between the electron-density-deficient region (so-called σ or π hole) of a covalently bonded halogen atom and a nucleophilic (Nu) site in the same (intramolecular) or another (intermolecular) molecular entity: R—Ha⋯Nu [Ha = F, Cl, Br or I; R = C, Pn (pnictogen), Ch (chalcogen), metal etc.; Nu = lone pair possessing Ha, Ch, Pn or metal atom, π-system, anion, radical, etc.; Cavallo et al., 2016 ]. Similarly to hydrogen and chalcogen bonds (Gurbanov et al., 2020 ; Mahmudov & Pombeiro, 2016 ), halogen bonds can also be classified into normal halogen bonds, positive charge-assisted halogen bonds, negative charge-assisted halogen bonds and charge-assisted halogen bonds (Peuronen et al., 2023 ). Both the strength and directionality of charge-assisted halogen bonds are much larger than those of normal halogen bonds (Gomila & Frontera, 2020 ; Shixaliyev et al., 2014 ), which are traditionally regarded as favourable synthetic tools for building new supramolecular systems (Mahmoudi et al., 2017a ,b ). In addition to their catalytic functions (Ma et al., 2021 ), N-oxide radicals can act as halogen-bond acceptors (Pang et al., 2013 ). In the context of this work, we investigated a new negative charge-assisted halogen-bonded supramolecular aggregate, which was obtained by the reaction of 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) with 1,2,3,4-tetrafluoro-5,6- diiodobenzene in the presence of CBr₄ in a mixture of hexane/CH₂Cl₂ at 343 K (see Fig. 1). We provide herein a detailed description of the synthesis and an examination of the molecular and crystal structures together with a Hirshfeld surface analysis of the title compound, (I).

Figure 1
Synthesis of 2,2,6,6-tetramethylpiperidin-1-ium bromide from 1,2,3,4-tetrafluoro-5,6-diiodobenzene.

2. Structural commentary

Two molecules are present in the asymmetric unit of the title compound, 2,2,6,6-tetramethyl piperidine-1-ium and 1,2,3,4-tetrafluoro-5,6-diiodobenzene, in addition to one uncoordinated bromide ion (Fig. 2). Atoms I1, I2, F1, F2, F3 and F4 are −0.0116 (3), −0.0287 (3), 0.005 (3), −0.022 (3), −0.003 (3) and 0.033 (3) Å, respectively, away from the best least-squares plane of the benzene ring (C1–C6). All atoms of the benzene derivative are essentially coplanar. The piperidine ring (N1/C7–C11), is in a chair conformation. There are no apparent unusual bond distances or interbond angles within the two molecules.

Figure 2
The title compound with atom-numbering scheme and 50% probability ellipsoids.

3. Supramolecular features

With regard to intermolecular contacts, the uncoordinated bromide ions link the 2,2,6,6-tetramethylpiperidine molecules through intermolecular C—H⋯Br and N—H⋯Br hydrogen bonds (Table 1) with a double or triple acceptor atom, resulting in dimers (Fig. 3). In the crystal, the dimers are stacked along the b-axis direction, while the coplanar 1,2,3,4-tetrafluoro-5,6-diiodobenzene molecules protrude along the c-axis direction, filling the space between the dimers (Fig. 4). There is a π–π interaction between the C1–C6 benzene rings with a centroid-to-centroid distance of 3.838 (3) Å, where the dihedral angle between the benzene rings is 10.5 (2)° with a slippage of 1.468 Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱⁱ	0.86 (2)	2.55 (2)	3.407 (3)	179 (4)
N1—H1B⋯Br1ⁱⁱⁱ	0.85 (2)	2.56 (2)	3.387 (3)	165 (5)
C13—H13C⋯Br1ⁱⁱ	0.98	2.91	3.767 (4)	147
Symmetry codes: (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Figure 3
The H⋯Br contacts leading to dimerization. Intermolecular C—H⋯Br and N—H⋯Br hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions are omitted for clarity.

Figure 4
A partial packing diagram, viewed down the b-axis direction. Intermolecular C—H⋯Br and N—H⋯Br hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions are omitted for clarity.

4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of the title compound (I), a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out using Crystal Explorer 17.5 (Spackman et al., 2021 ). The contact distances d_i and d_e from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of d_norm. The combination of d_i and d_e in the form of two-dimensional fingerprint plots (McKinnon et al., 2004 ) provides a summary of intermolecular contacts in the crystal. In the HS plotted over d_norm (Fig. 5), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (no/weak contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The bright-red spots are indicative of their roles as the respective donors and/or acceptors. The shape-index would represent any C—H⋯π interaction as red depressions located at the π-ring system and a blue region surrounding the respective C—H moiety, and hence Fig. 6 clearly suggests that there are no such C—H⋯π interactions present in (I). The shape-index of the HS can also indicate π–π stacking interactions by the presence of adjacent red and blue triangles. Fig. 6 suggests π–π interactions are present in (I).

Figure 5
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm.

Figure 6
Hirshfeld surface of the title compound plotted over shape-index.

The overall two-dimensional fingerprint plot is shown in Fig. 7a and those delineated into H⋯F/F⋯H, H⋯H, H⋯Br/Br⋯H, H⋯I/I⋯H, F⋯I/I⋯F, C⋯I/I⋯C, C⋯C, F⋯F, H⋯C/C⋯H, I⋯I and F⋯Br/Br⋯F contacts (McKinnon et al., 2007 ) are illustrated in Fig. 7b–l, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction clearly is of the H⋯F/F⋯H type (Table 2), contributing 23.8% to the overall crystal packing, which is reflected in Fig. 7b as pair of spikes with tips at d_e + d_i = 2.52 Å. The H⋯H interactions (Fig. 7c) contribute 22.6% to the HS and form a single maximum extension at d_e = d_i = 1.18 Å. The H⋯Br/Br⋯H (Fig. 7d) and H⋯I/I⋯H (Fig. 7e) contacts contribute 17.3% and 13.8%, respectively, to the HS, appearing as pairs of spikes with the tips at d_e + d_i = 2.36 Å and d_e + d_i = 3.04 Å, respectively. The F⋯I/I⋯F contacts (Fig. 7f) make a 7.5% contribution to the HS and have the tips at d_e + d_i = 3.74 Å. The C⋯I/I⋯C contacts (Fig. 7g) contribute 5.6%, the pair of spikes having tips at d_e + d_i = 3.70 Å. The C⋯C contacts (Fig. 7h) contribute 4.1% to the HS and have a bullet-shaped distribution of points with the tip at d_e = d_i = 1.68 Å. Finally, the F⋯F (Fig. 7i), H⋯C/C⋯H (Fig. 7j), I⋯I (Fig. 7k), F⋯Br/Br⋯F (Fig. 7l) and F⋯C/C⋯F (not shown) contacts make 1.7%, 1.0%, 0.9%, 0.9% and 0.8% contributions, respectively, to the HS and have very low densities of points.

Table 2
Selected interatomic distances (Å)

I1⋯F4	3.138 (3)	C11⋯H14B	2.83
I1⋯I2	3.7118 (4)	C12⋯H11B	2.83
I2⋯F1	3.111 (3)	C12⋯H14B	2.67
I1⋯H15Cⁱ	3.16	C14⋯H12B	2.72
H1A⋯Br1ⁱⁱ	2.546 (19)	C14⋯H11B	2.90
H13C⋯Br1ⁱⁱ	2.91	H1A⋯H13C	2.21
H1B⋯Br1ⁱⁱⁱ	2.56 (2)	H1A⋯H15C	2.30
F1⋯F2	2.670 (4)	H1B⋯H12C	2.19
F2⋯F3	2.709 (4)	H1B⋯H14A	2.34
F3⋯F4	2.654 (4)	H7B⋯H15C	2.40
F2⋯H12A	2.65	H11B⋯H12B	2.19
H11A⋯F3^iv	2.63	H11B⋯H14B	2.29
C12⋯C14	3.203 (6)	H12B⋯H14B	1.97
C11⋯H12B	2.76
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 7
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯F/F⋯H, (c) H⋯H, (d) H⋯Br/Br⋯H, (e) H⋯I/ ⋯H, (f) F⋯I/I⋯F, (g) C⋯I/I⋯C, (h) C⋯C, (i) F⋯F, (j) H⋯C/C⋯H, (k) I⋯I, and (l) F⋯Br/Br⋯F interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

The nearest neighbour coordination environment of a molecule can be determined from the colour patches on the HS based on how close to other molecules they are. The Hirshfeld surface representations with the fragment patches plotted onto the surface are shown for the H⋯F/F⋯H, H⋯H, H·· Br/Br⋯H and H⋯I/I⋯H interactions in Fig. 8a–d, respectively.

Figure 8
Hirshfeld surface representations of contact patches plotted onto the surface for (a) H⋯F/F⋯H, (b) H⋯H, (c) H⋯Br/Br⋯H and (d) H⋯I/I⋯H interactions.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the crystal packing. The large number of H⋯F/F⋯H, H⋯H, H⋯Br/Br⋯H and H⋯I/I⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the packing (Hathwar et al., 2015 ).

5. Database survey

A survey of the Cambridge Structural Database (CSD, Version 5.42, last updated February 2023; Groom et al., 2016 ) considering both ring motifs indicates that only one molecular structure is closely related to the title compound (I), viz. 1-oxy-2,2,6,6-tetramethylpiperidin-4-yl radical benzoate bis(1,2,3,4-tetrafluoro-5, 6-diiodobenzene), C₁₆H₂₂NO₃·2C₆F₄I₂ (CSD refcode HISZEQ; Pang et al., 2013). The C₆F₄I₂ molecules are essentially identical in their metrical parameters in both structures, while the aliphatic ring system in HISZEQ bears more substituents than in the title compound (I) resulting in small deviations of the overall geometries of the two respective six-membered rings.

6. Synthesis and crystallization

TEMPO (10 mmol), 1,2,3,4-tetrafluoro-5,6-diiodobenzene (10 mmol) and CBr₄ (10 mmol) were dissolved in 30 ml of hexane/CH₂Cl₂ (v/v, 1:1), refluxed for 2 h, and left for slow evaporation. Orange crystals of the product started to form after 2 d at room temperature; they were filtered off and dried in air. Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution. Yield 61% (based on TEMPO), orange powder soluble in methanol, ethanol and DMSO. Analysis calculated for C₁₅H₂₀BrF₄I₂N (M_r = 624.04): C, 28.87; H, 3.23; N, 2.24. Found: C, 28.82; H, 3.20; N, 2.20. ¹H NMR (DMSO-d⁶), δ: 8.08 (2N–H), 1.73 (2CH₂), 1.65 (CH₂), 1.31 (4CH₃). ¹³C NMR (DMSO-d⁶), 15.6 (CH₂), 26.9 (4CH₃), 34.4 (2CH₂), 57.2 [2C(CH₃)₂], 90.5 (2C—I), 148.1 (4C—F).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The N-bound hydrogen atoms were located in a difference-Fourier map, and refined by applying restraints (DFIX). The C-bound H-atom positions were calculated geometrically at distances of 0.99 Å (for CH₂) and 0.98 Å (for CH₃) and refined using a riding model with U_iso(H) = k × U_eq(C), where k = 1.2 for CH₂ hydrogen atoms and k = 1.5 for CH₃ hydrogen atoms. Two reflections were omitted as clear outliers.

Table 3
Experimental details

Crystal data
Chemical formula	C₉H₂₀N⁺·Br⁻·C₆F₄I₂
M_r	624.03
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	29.0324 (8), 9.1477 (2), 15.0296 (4)
β (°)	108.533 (1)
V (Å³)	3784.56 (17)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	5.47
Crystal size (mm)	0.25 × 0.21 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.342, 0.423
No. of measured, independent and observed [I > 2σ(I)] reflections	14152, 3877, 3480
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.069, 1.10
No. of reflections	3877
No. of parameters	220
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.50, −0.69
Computer programs: APEX4 and SAINT (Bruker, 2014 ), SHELXT2019/1 (Sheldrick, 2015a ), SHELXL2019/1 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2405482

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024011502/yz2062sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024011502/yz2062Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024011502/yz2062Isup3.cml

checkCIF report

Computing details top

(I) top

Crystal data top

C₉H₂₀N⁺·Br⁻·C₆F₄I₂	F(000) = 2352
M_r = 624.03	D_x = 2.190 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 29.0324 (8) Å	Cell parameters from 8061 reflections
b = 9.1477 (2) Å	θ = 2.4–26.4°
c = 15.0296 (4) Å	µ = 5.47 mm⁻¹
β = 108.533 (1)°	T = 150 K
V = 3784.56 (17) Å³	Prism, orange
Z = 8	0.25 × 0.21 × 0.19 mm

Data collection top

Bruker APEXII CCD diffractometer	3480 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.022
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.5°, θ_min = 2.6°
T_min = 0.342, T_max = 0.423	h = −36→33
14152 measured reflections	k = −11→11
3877 independent reflections	l = −18→18

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0297P)² + 23.4044P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.003
3877 reflections	Δρ_max = 1.50 e Å⁻³
220 parameters	Δρ_min = −0.69 e Å⁻³

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
I1	0.58724 (2)	0.50666 (3)	0.95416 (2)	0.02186 (8)
I2	0.49598 (2)	0.20828 (3)	0.88878 (2)	0.03147 (9)
Br1	0.70229 (2)	0.44644 (4)	1.06238 (3)	0.02025 (10)
F1	0.39660 (9)	0.3559 (3)	0.7874 (2)	0.0358 (6)
F2	0.36882 (9)	0.6336 (3)	0.7483 (2)	0.0385 (7)
F3	0.43515 (10)	0.8520 (3)	0.7953 (2)	0.0402 (7)
F4	0.52828 (10)	0.7943 (3)	0.8811 (2)	0.0350 (6)
N1	0.20902 (12)	0.4228 (4)	0.5387 (2)	0.0168 (7)
C1	0.41559 (15)	0.6043 (5)	0.7915 (3)	0.0273 (10)
C2	0.43063 (15)	0.4616 (5)	0.8126 (3)	0.0251 (9)
C3	0.47865 (15)	0.4272 (5)	0.8587 (3)	0.0223 (8)
C4	0.51296 (14)	0.5399 (5)	0.8839 (3)	0.0208 (8)
C5	0.49698 (15)	0.6813 (5)	0.8607 (3)	0.0247 (9)
C6	0.44896 (16)	0.7134 (5)	0.8155 (3)	0.0285 (10)
C7	0.12586 (15)	0.4790 (5)	0.5367 (3)	0.0258 (9)
H7A	0.095235	0.529016	0.501617	0.031*
H7B	0.117866	0.376129	0.546160	0.031*
C8	0.16011 (14)	0.4814 (4)	0.4774 (3)	0.0203 (8)
C9	0.23227 (14)	0.4809 (4)	0.6381 (3)	0.0200 (8)
C10	0.19400 (15)	0.4749 (5)	0.6869 (3)	0.0241 (9)
H10A	0.207115	0.520952	0.749488	0.029*
H10B	0.186794	0.371383	0.696339	0.029*
C11	0.14695 (15)	0.5518 (5)	0.6321 (3)	0.0270 (9)
H11A	0.123373	0.545906	0.667202	0.032*
H11B	0.153481	0.656302	0.623706	0.032*
C12	0.25235 (15)	0.6339 (5)	0.6354 (3)	0.0261 (9)
H12A	0.273188	0.661239	0.698410	0.039*
H12B	0.225401	0.703502	0.614153	0.039*
H12C	0.271380	0.635554	0.592027	0.039*
C13	0.27448 (14)	0.3797 (5)	0.6841 (3)	0.0249 (9)
H13A	0.289234	0.407421	0.750087	0.037*
H13B	0.298770	0.387430	0.651613	0.037*
H13C	0.262726	0.278711	0.680484	0.037*
C14	0.16547 (16)	0.6325 (5)	0.4403 (3)	0.0290 (10)
H14A	0.191404	0.631076	0.411518	0.043*
H14B	0.173643	0.702913	0.492089	0.043*
H14C	0.134833	0.661096	0.393177	0.043*
C15	0.14272 (15)	0.3773 (5)	0.3950 (3)	0.0245 (9)
H15A	0.165817	0.377765	0.359601	0.037*
H15B	0.110710	0.408459	0.354083	0.037*
H15C	0.140398	0.278296	0.418190	0.037*
H1A	0.2074 (14)	0.330 (2)	0.544 (3)	0.010 (10)*
H1B	0.2309 (15)	0.451 (6)	0.517 (4)	0.040 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01724 (13)	0.02663 (16)	0.02143 (14)	−0.00053 (10)	0.00575 (10)	−0.00051 (11)
I2	0.03171 (16)	0.02433 (16)	0.03802 (18)	−0.00134 (12)	0.01060 (13)	0.00187 (12)
Br1	0.01935 (19)	0.0180 (2)	0.0230 (2)	0.00066 (15)	0.00620 (16)	−0.00154 (16)
F1	0.0249 (13)	0.0378 (16)	0.0414 (16)	−0.0114 (12)	0.0058 (12)	0.0024 (13)
F2	0.0188 (12)	0.0524 (18)	0.0406 (16)	0.0086 (12)	0.0040 (11)	0.0072 (14)
F3	0.0398 (15)	0.0286 (15)	0.0507 (18)	0.0130 (12)	0.0121 (14)	0.0063 (14)
F4	0.0361 (14)	0.0235 (14)	0.0428 (16)	−0.0082 (11)	0.0091 (12)	−0.0004 (12)
N1	0.0200 (17)	0.0119 (17)	0.0199 (17)	−0.0013 (13)	0.0083 (14)	0.0011 (13)
C1	0.020 (2)	0.041 (3)	0.022 (2)	0.0036 (18)	0.0077 (17)	0.0035 (19)
C2	0.020 (2)	0.035 (2)	0.021 (2)	−0.0069 (18)	0.0077 (17)	0.0000 (18)
C3	0.025 (2)	0.023 (2)	0.019 (2)	0.0004 (17)	0.0087 (17)	0.0012 (17)
C4	0.0174 (19)	0.026 (2)	0.020 (2)	−0.0006 (16)	0.0067 (16)	−0.0018 (17)
C5	0.025 (2)	0.029 (2)	0.022 (2)	−0.0012 (18)	0.0087 (17)	−0.0022 (18)
C6	0.029 (2)	0.032 (3)	0.026 (2)	0.0066 (19)	0.0115 (19)	0.0037 (19)
C7	0.020 (2)	0.026 (2)	0.030 (2)	0.0017 (17)	0.0072 (18)	0.0010 (19)
C8	0.0186 (19)	0.017 (2)	0.025 (2)	0.0028 (15)	0.0069 (16)	0.0021 (17)
C9	0.0211 (19)	0.020 (2)	0.0185 (19)	−0.0034 (16)	0.0057 (16)	−0.0031 (16)
C10	0.026 (2)	0.026 (2)	0.024 (2)	−0.0024 (17)	0.0127 (18)	−0.0027 (18)
C11	0.025 (2)	0.029 (2)	0.030 (2)	0.0013 (18)	0.0128 (18)	−0.0042 (19)
C12	0.022 (2)	0.024 (2)	0.034 (2)	−0.0055 (17)	0.0112 (18)	−0.0086 (19)
C13	0.021 (2)	0.029 (2)	0.023 (2)	0.0007 (17)	0.0048 (17)	−0.0022 (18)
C14	0.031 (2)	0.020 (2)	0.034 (2)	0.0040 (18)	0.0088 (19)	0.0077 (19)
C15	0.024 (2)	0.023 (2)	0.023 (2)	−0.0002 (17)	0.0030 (17)	0.0022 (17)

Geometric parameters (Å, º) top

I1—C4	2.100 (4)	C8—C14	1.517 (6)
I2—C3	2.080 (4)	C9—C10	1.514 (5)
F1—C2	1.348 (5)	C9—C13	1.516 (6)
F2—C1	1.333 (5)	C9—C12	1.522 (6)
F3—C6	1.335 (5)	C10—C11	1.525 (6)
F4—C5	1.346 (5)	C10—H10A	0.9900
N1—C8	1.523 (5)	C10—H10B	0.9900
N1—C9	1.526 (5)	C11—H11A	0.9900
N1—H1A	0.860 (19)	C11—H11B	0.9900
N1—H1B	0.846 (19)	C12—H12A	0.9800
C1—C6	1.357 (7)	C12—H12B	0.9800
C1—C2	1.381 (7)	C12—H12C	0.9800
C2—C3	1.382 (6)	C13—H13A	0.9800
C3—C4	1.399 (6)	C13—H13B	0.9800
C4—C5	1.381 (6)	C13—H13C	0.9800
C5—C6	1.375 (6)	C14—H14A	0.9800
C7—C11	1.522 (6)	C14—H14B	0.9800
C7—C8	1.531 (6)	C14—H14C	0.9800
C7—H7A	0.9900	C15—H15A	0.9800
C7—H7B	0.9900	C15—H15B	0.9800
C8—C15	1.516 (6)	C15—H15C	0.9800

I1···F4	3.138 (3)	C11···H14B	2.83
I1···I2	3.7118 (4)	C12···H11B	2.83
I2···F1	3.111 (3)	C12···H14B	2.67
H1A···Br1ⁱ	2.56	C14···H12B	2.72
H13C···Br1ⁱ	2.91	C14···H11B	2.90
H1B···Br1ⁱⁱ	2.58 (5)	H1A···H13C	2.22
F1···F2	2.670 (4)	H1A···H15C	2.30
F2···F3	2.709 (4)	H1B···H12C	2.16
F3···F4	2.654 (4)	H1B···H14A	2.32
F2···H12A	2.65	H7B···H15C	2.40
H11A···F3ⁱⁱⁱ	2.63	H11B···H12B	2.19
C12···C14	3.203 (6)	H11B···H14B	2.27
C11···H12B	2.76	H12B···H14B	1.97

C8—N1—C9	120.4 (3)	C10—C9—N1	107.3 (3)
C8—N1—H1A	110 (3)	C13—C9—N1	106.0 (3)
C9—N1—H1A	106 (3)	C12—C9—N1	110.4 (3)
C8—N1—H1B	109 (4)	C9—C10—C11	113.0 (4)
C9—N1—H1B	97 (4)	C9—C10—H10A	109.0
H1A—N1—H1B	114 (5)	C11—C10—H10A	109.0
F2—C1—C6	120.8 (4)	C9—C10—H10B	109.0
F2—C1—C2	120.1 (4)	C11—C10—H10B	109.0
C6—C1—C2	119.2 (4)	H10A—C10—H10B	107.8
F1—C2—C1	117.6 (4)	C7—C11—C10	109.3 (3)
F1—C2—C3	120.7 (4)	C7—C11—H11A	109.8
C1—C2—C3	121.7 (4)	C10—C11—H11A	109.8
C2—C3—C4	119.1 (4)	C7—C11—H11B	109.8
C2—C3—I2	117.7 (3)	C10—C11—H11B	109.8
C4—C3—I2	123.3 (3)	H11A—C11—H11B	108.3
C5—C4—C3	117.9 (4)	C9—C12—H12A	109.5
C5—C4—I1	118.1 (3)	C9—C12—H12B	109.5
C3—C4—I1	124.0 (3)	H12A—C12—H12B	109.5
F4—C5—C6	117.0 (4)	C9—C12—H12C	109.5
F4—C5—C4	120.9 (4)	H12A—C12—H12C	109.5
C6—C5—C4	122.1 (4)	H12B—C12—H12C	109.5
F3—C6—C1	120.0 (4)	C9—C13—H13A	109.5
F3—C6—C5	119.9 (4)	C9—C13—H13B	109.5
C1—C6—C5	120.0 (4)	H13A—C13—H13B	109.5
C11—C7—C8	113.6 (4)	C9—C13—H13C	109.5
C11—C7—H7A	108.8	H13A—C13—H13C	109.5
C8—C7—H7A	108.8	H13B—C13—H13C	109.5
C11—C7—H7B	108.8	C8—C14—H14A	109.5
C8—C7—H7B	108.8	C8—C14—H14B	109.5
H7A—C7—H7B	107.7	H14A—C14—H14B	109.5
C15—C8—C14	108.6 (4)	C8—C14—H14C	109.5
C15—C8—N1	106.1 (3)	H14A—C14—H14C	109.5
C14—C8—N1	111.0 (3)	H14B—C14—H14C	109.5
C15—C8—C7	110.9 (3)	C8—C15—H15A	109.5
C14—C8—C7	112.9 (3)	C8—C15—H15B	109.5
N1—C8—C7	107.2 (3)	H15A—C15—H15B	109.5
C10—C9—C13	111.6 (3)	C8—C15—H15C	109.5
C10—C9—C12	113.1 (3)	H15A—C15—H15C	109.5
C13—C9—C12	108.2 (3)	H15B—C15—H15C	109.5

F2—C1—C2—F1	0.4 (6)	C2—C1—C6—C5	−0.4 (6)
C6—C1—C2—F1	−179.7 (4)	F4—C5—C6—F3	−1.2 (6)
F2—C1—C2—C3	−178.9 (4)	C4—C5—C6—F3	179.3 (4)
C6—C1—C2—C3	1.0 (6)	F4—C5—C6—C1	179.0 (4)
F1—C2—C3—C4	−179.9 (4)	C4—C5—C6—C1	−0.6 (7)
C1—C2—C3—C4	−0.6 (6)	C9—N1—C8—C15	−166.9 (3)
F1—C2—C3—I2	−0.7 (5)	C9—N1—C8—C14	75.4 (4)
C1—C2—C3—I2	178.6 (3)	C9—N1—C8—C7	−48.4 (4)
C2—C3—C4—C5	−0.4 (6)	C11—C7—C8—C15	166.3 (4)
I2—C3—C4—C5	−179.5 (3)	C11—C7—C8—C14	−71.7 (5)
C2—C3—C4—I1	180.0 (3)	C11—C7—C8—N1	50.9 (5)
I2—C3—C4—I1	0.9 (5)	C8—N1—C9—C10	49.8 (4)
C3—C4—C5—F4	−178.6 (4)	C8—N1—C9—C13	169.1 (3)
I1—C4—C5—F4	1.1 (5)	C8—N1—C9—C12	−73.8 (4)
C3—C4—C5—C6	1.0 (6)	C13—C9—C10—C11	−169.0 (4)
I1—C4—C5—C6	−179.4 (3)	C12—C9—C10—C11	68.7 (5)
F2—C1—C6—F3	−0.4 (6)	N1—C9—C10—C11	−53.2 (4)
C2—C1—C6—F3	179.7 (4)	C8—C7—C11—C10	−58.9 (5)
F2—C1—C6—C5	179.5 (4)	C9—C10—C11—C7	60.2 (5)

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, y, −z+3/2; (iii) −x+1/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.86 (2)	2.55 (2)	3.409 (3)	179 (4)
N1—H1B···Br1ⁱⁱ	0.85 (2)	2.58 (3)	3.387 (3)	161 (5)
C13—H13C···Br1ⁱ	0.98	2.91	3.769 (4)	146

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

Acknowledgements

The authors' contributions are as follows. Conceptualization, AVG, TH and ANB; synthesis, AVG and GZM; X-ray analysis, AVG; writing (review and editing of the manuscript) AVG and TH; funding acquisition, AVG, GZM, KIH and TAJ; supervision, AVG, TH and ANB.

Funding information

This work was supported by the Fundaçao para a Ciencia e a Tecnologia (FCT, Portugal), projects UIDB/00100/2020 (https://doi.org/10.54499/UIDB/00100/2020) and UIDP/00100/2020 (https://doi.org/10.54499/UIDP/00100/2020) of the Centro de Quimica Estrutural and LA/P/0056/2020 (https://doi.org/10.54499/LA/P/0056/2020) of the Institute of Molecular Sciences, as well as Baku State University, Baku Engineering University, Azerbaijan Medical University, Western Caspian University and Khazar University in Azerbaijan. TH is also grateful to the Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

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