Crystal structure and Hirshfeld surface analysis of 10-(3-benzyl­thio­phen-2-yl)-5,5-di­fluoro-5H-4λ4,5λ4-di­pyrrolo­[1,2-c:2′,1′-f][1,3,2]di­aza­borinine

Polianskaia, Z.A.; Larionov, A.S.; Khrustalev, V.N.; Akkurt, M.; Manahelohe, G.M.; Guliyeva, N.A.; Hasanov, K.I.

doi:10.1107/S2056989026003889

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ISSN: 2056-9890

Volume 82| Part 5| May 2026| Pages 505-510

https://doi.org/10.1107/S2056989026003889

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Crystal structure and Hirshfeld surface analysis of 10-(3-benzylthiophen-2-yl)-5,5-difluoro-5H-4λ⁴,5λ⁴-dipyrrolo[1,2-c:2′,1′-f][1,3,2]diazaborinine

Zlata A. Polianskaia,^a Artem S. Larionov,^a Victor N. Khrustalev,^a,^b Mehmet Akkurt,^c Gizachew Mulugeta Manahelohe,^d ^* Narmina A. Guliyeva ^e and Khudayar I. Hasanov ^f

^aRUDN University, 6 Miklukho-Maklaya St., Moscow 117198, Russian Federation, ^bZelinsky Institute of Organic Chemistry of RAS, Leninsky Prospect 47, Moscow 119991, Russian Federation, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, ^dDepartment of Chemistry, University of Gondar, PO Box 196, Gondar, Ethiopia, ^eDepartment of Chemical Engineering, Baku Engineering University, Khirdalan Hasan Aliyev str. 120, Baku, Absheron AZ0101, Azerbaijan, and ^fAzerbaijan Medical University, Scientific Research Centre (SRC), A. Kasumzade St. 14, AZ 1022, Baku, Azerbaijan
^*Correspondence e-mail: [email protected]

Edited by T. Akitsu, Tokyo University of Science, Japan (Received 17 March 2026; accepted 13 April 2026; online 29 April 2026)

In the title compound, C₂₀H₁₅BF₂N₂S, the twelve-membered ring system is essentially planar (r.m.s. deviation = 0.001 Å). The dihedral angles between the average plane of this ring and the thiophene and phenyl rings are 58.69 (4) and 61.41 (4)°, respectively. In the crystal, C—H⋯F interactions generate R²₂(10) and three types of R²₃(21) ring motifs around a molecule, resulting in layers parallel to the (101) plane. The molecules further form layers parallel to the (101) plane through C—H⋯π interactions. According to a Hirshfeld surface analysis, H⋯H (41.5%), C⋯H/H⋯C (23.5%) and F⋯H/H⋯F (18.2%) interactions are the most significant contributors to the crystal packing.

Keywords: crystal structure; C—H⋯F interactions; C—H⋯π interactions; Hirshfeld surface analysis.

CCDC reference: 2545790

1. Chemical context

4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) complexes represent one of the most versatile classes of small-molecule fluorophores, renowned for their exceptional photophysical properties (Ulrich et al., 2008 ; Loudet & Burgess, 2007 ). These properties include high molar absorption coefficients, sharp fluorescence emission peaks with high quantum yields, and remarkable chemical and photochemical stability (Boens et al., 2019 ; Ni & Wu, 2014 ). Consequently, BODIPY derivatives have found extensive applications across diverse fields, functioning as fluorescent sensors for bioimaging, agents for photodynamic therapy, laser dyes, and photocatalysts (Poddar & Misra, 2020 ; Martynov & Pakhomov, 2021 ; Wang et al., 2023 ). A key feature that underpins their versatility is the ability to fine-tune their spectroscopic characteristics through rational structural modification of the dipyrromethene core (Waly et al., 2022 ; Lu et al., 2014 ). The photophysical behavior of BODIPY is highly sensitive to the nature of the substituent at the meso-position (C-8), which plays a critical role in the molecule's electronic distribution (Ozdemir et al., 2014 ; Lincoln et al., 2014 ). While the introduction of aryl substituents at this position is well-documented (Spector et al., 2024 ), replacing the six-membered ring with five-membered aromatic heterocycles, which can lead to the further modulation the electronic properties, are poorly studied. Studies of meso-substituted BODIPY with such heterocycles as furan, thiophene, pyrrole and selenophene were firstly carried out and demonstrated that this substitution results in a more planar conformation between the heterocycle and the dipyrromethene framework, extending π-conjugation and leading to notable bathochromic shifts in absorption and emission spectra, as well as changes in fluorescence quantum yields, compared to their meso-aryl counterparts (Kim et al., 2010 ; Sharma et al., 2016 ). In this work, we describe the synthesis of a new BODIPY derivative bearing a thiophene moiety at the meso-position to explore its impact on the structural, electronic, and photophysical characteristics of the resulting fluorophore. In continuation of our studies on five-membered-heterocycle-substituted dipyrrolmethanes, the recently described 3-benzyl-2-[bis(1H-pyrrol-2-yl)methyl]thiophene, 1 (Sadikhova et al., 2024 ) was utilized as a key precursor. Oxidation with DDQ in CH₂Cl₂ (30 min), followed by neutralization with DIPEA and subsequent treatment with BF₃·OEt₂, provided the corresponding BODIPY complex. The target meso-thienyl-substituted BODIPY, 2, was isolated in 40% yield after silica gel column chromatography (Fig. 1).

Figure 1
Synthesis of 10-(3-benzylthiophen-2-yl)-5,5-difluoro-5H-4λ⁴,5λ⁴-dipyrrolo[1,2-c:2′,1′-f][1,3,2]diazaborinine, 2.

2. Structural commentary

In the title compound (Fig. 2), the twelve-membered ring system (B1/N1/N2/C1–C9) is essentially planar (r.m.s. deviation = 0.001 Å). The dihedral angles between the average plane of this ring and the thiophene (S1/C10–C13) and phenyl (C15–C20) rings are 58.69 (4) and 61.41 (4)°, respectively. The thiophene and phenyl rings subtend an angle of 81.50 (5)°. The F2—B1—F1 angle is 109.39 (8)°. The bond lengths and angles in the title compound are in good agreement with those in the compounds discussed in the Database survey section.

Figure 2
Molecular structure of the title compound showing the atom labelling and ellipsoids at the 30% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, C—H⋯F interactions form R₂²(10) and three types of R₃²(21) ring motifs (Bernstein et al. 1995 ; Tables 1 and 2; Figs. 3, 4 and 5) around a molecule, leading to the formation of layers parallel to the (101) plane. The molecules are additionally connected by C—H⋯π interactions, forming layers parallel to the (10 $[\overline{1}]$ ) plane (Table 1; Figs. 6 and 7).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the S1/C10–C13 and N1/C1–C4 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯F2ⁱ	0.95	2.36	3.2017 (12)	148
C13—H13⋯F2ⁱⁱ	0.95	2.55	3.3113 (12)	137
C20—H20⋯F2ⁱⁱⁱ	0.95	2.51	3.3221 (13)	144
C14—H14B⋯Cg2ⁱⁱⁱ	0.99	2.81	3.5815 (11)	135
C18—H18⋯Cg1^iv	0.95	2.92	3.7764 (13)	151
Symmetry codes: (i) ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) .

Table 2
Summary of short interatomic contacts (Å)

Contact	Distance	Symmetry operation
H8⋯F1	2.70	1 + x, y, z
F2⋯H20	2.51	$[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
H18⋯C13	2.87	1 − x, 1 − y, 1 − z
H9⋯F2	2.36	1 − x, 1 − y, 2 − z
F2⋯H13	2.55	− $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z
H1⋯C17	2.80	$[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
H9⋯H8	2.52	2 − x, 1 − y, 2 − z
H19⋯H13	2.53	2 − x, 1 − y, 1 − z
H8⋯H19	2.54	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z

Figure 3
The C—H⋯F interactions of the title compound showing the ring motifs. Symmetry codes: (a) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z; (b) 1 − x, 1 − y, 2 − z; (c) − $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z; (d) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z; (e) $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z.

Figure 4
Crystal packing along the a axis showing C—H⋯F interactions (dashed lines).

Figure 5
View of the C—H⋯F interactions in Fig. 4

along the b axis.

Figure 6
Crystal packing along the a axis showing C—H⋯π interactions (dashed lines).

Figure 7
View of the C—H⋯π interactions in Fig. 6

along the b axis.

A Hirshfeld surface analysis was conducted using Crystal Explorer 17.5 (Spackman et al., 2021 ) to view and quantify intermolecular interactions, and to create the corresponding two-dimensional fingerprint plots. The Hirshfeld surfaces were mapped over d_norm in the range −0.2379 (red) to +1.5528 (blue) a.u. (Fig. 8). The most important intermolecular interactions are the H⋯H interaction (41.5%), which appear at the central region of the fingerprint plot with d_e = d_i ≃ 1.15 Å (Fig. 9b). The reciprocal C⋯H/H⋯C interactions appear as two symmetrical broad wings with d_e + d_i ≃ 2.75 Å and contribute 23.5% to the Hirshfeld surface (Fig. 9c). The reciprocal F⋯H/H⋯F interaction with an 18.2% contribution is present as sharp symmetrical wings at diagonal axes d_e + d_i ≃ 2.2 (Fig. 9d). Other smaller contributions are made by S⋯H/H⋯S (6.2%), C⋯C (4.2%), N⋯H/H⋯N (2.3%), S⋯C/C⋯S (1.8%), S⋯N/N⋯S (0.9%), S⋯F/F⋯S (0.6%), N⋯C/C⋯N (0.5%) and F⋯F (0.2%) interactions.

Figure 8
The three-dimensional Hirshfeld surface for the title compound, plotted over d_norm, showing C—H⋯F interactions (dashed lines).

Figure 9
The two-dimensional fingerprint plots for the title molecule showing (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C and (d) F⋯H/H⋯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.

4. Database survey

A search in the Cambridge Structural Database (CSD, version 6.00, update April 2025; Groom et al., 2016 ) for 2,2-difluoro-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12)\,4,6,8,10-pentaene (twelve-membered ring moiety) gives thirteen hits, viz. I (DUTLOX: Shchevnikov et al., 2025 ), II (GATDIQ: Khan & Ravikanth, 2012 ), III (GATDOW: Khan & Ravikanth, 2012), IV (KETDAQ: Jun et al., 2012a ), V (NARSAC: Khan et al., 2012), VI (NARSEG: Khan et al., 2012), VII (ROZGEU: Zhao et al., 2015 ), VIII (ROZHAR: Zhao et al., 2015), IX (ROZHEV: Zhao et al., 2015), X (UKANUQ: Kim et al., 2010), XI (UKANUQ01: Khan et al., 2012), XII (ULAQOP: Sharma et al., 2016) and XIII (XELDAV: Jun et al., 2012b ).

II, III, VII and VIII crystallize in the triclinic space group P $[\overline{1}]$ . IV and XII crystallize in the orthorhombic space groups Pbca and Pna2₁, respectively. V, IX, X and XI crystallize in the monoclinic space group P2₁/c, while VI, XIII and I crystallize in the monoclinic space groups P2₁/n, C2/c and C2/c, respectively.

The dihedral angle between the two ring systems (furan/thiophene substituent and twelve-membered ring moiety) varies between 25.93 (10) and 88.13 (14)°, and is influenced by the substitution pattern and molecular environment. In I, a thiophene ring is affixed to the twelve-membered ring system, whilst the others are connected to a furan ring. In I 33.34 (6)°, in II, with two independent molecules in the asymmetric unit, the dihedral angles are 33.31 (10) and 33.85 (9)°, in III 44.4 (5)°, in IV 88.13 (14)°, in VIII 84.82 (8)°, in IX 78.02 (9)°, in XII 31.24 (16)°, in XIII 75.60 (13)°, and in V, with two independent molecules in the asymmetric unit, 29.4 (2) and 32.2 (2)°, respectively. In VI, the furan ring is disordered over two positions, the dihedral angles are 83.0 (3) and 36.9 (2)°, respectively. In X, with two independent molecules in the asymmetric unit, the dihedral angles are 26.59 (16) and 26.92 (17)°, with similar values for XI [26.65 (10) and 25.93 (10)°].

In IV, VII and IX, C—H⋯F intramolecular interactions are observed, while in VIII there are C—H⋯S and C—H⋯F interactions. In the remaining compounds, there are intramolecular C—H⋯O hydrogen bonds involving the O atom of the furan ring. Additionally, in VI and XII, besides C—H⋯O, there are also C—H⋯F interactions, and in XIII, intramolecular C—H⋯S interactions are present as well.

In compounds I, II, III, V, VI, VII, X, XI, XII, and XIII, the intramolecular C—H⋯O interactions have H⋯O distances ranging from 2.29 to 2.05 Å, and C—H⋯O angles ranging from 109 to 169°. In compounds II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, and XIII, the intramolecular C—H⋯F interactions have H⋯F distances ranging from 2.29 to 2.55 Å, and C—H⋯F angles ranging from 110 to 179°. In compounds VIII and XIII, the intramolecular C—H⋯S interactions have H⋯S distances ranging from 2.77 to 2.85 Å, and C—H⋯S angles ranging from 105 to 111°. Intramolecular interactions can arise from the presence of different components attached to the main group of the molecules.

5. Synthesis and crystallization

The BODIPY synthesis procedure was reported previously (Shchevnikov et al., 2025). Dipyrrolmethane 1 (Sadikhova et al., 2024) (418 mg, 1.3 mmol) was dissolved in dry DCM (20 mL), after that 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ, 890 mg, 3.9 mmol) was added; the reaction mixture was stirred for 30 min at r.t (TLC control), poured into water (50 mL) and extracted with DCM (3 × 30 mL). The organic layer was dried with anhydrous Na₂SO₄, concentrated in vacuo and the residue was dissolved in dry DCM (20 mL). Boron trifluoride etherate (3.3 ml, 26.3 mmol) and an equal volume of diisopropylethylamine (DIPEA, 3.3 ml) were added to the solution. The reaction mixture was stirred at r.t. for 1 h (TLC control) and then poured into water (50 mL), extracted with DCM (3 × 30 mL) and washed with saturated Na₂CO₃ (3 × 30 mL). The organic layer was dried with anhydrous Na₂SO₄, the target product 2 was purified by column chromatography (eluent: ethyl acetate/hexane 1:10) to give red crystals, yield 40%, 188 mg (0.52 mmol), m.p. 407–409 K. Single crystals of the title compound were grown from a mixture of ethyl acetate/hexane. IR (KBr), ν (cm⁻¹): 1551, 1410, 1386, 1110, 1074, 828. ¹H NMR (700.2 MHz, CDCl₃) (J, Hz): δ 7.93 (br.s, 2H, H Pyr), 7.49 (d, J = 5.25 Hz, 1H, H-5 Thien), 7.21 (t, J = 7.39 Hz, 2H, H-3,5 Ph), 7.15 (t, J = 7.39 Hz, 1H, H-4 Ph), 7.01–6.98 (m, 5H, H Aryl + H Pyr + H-4 Thien), 6.54 (m, 2H, H Pyr), 3.96 (s, 2H, CH₂).¹³C NMR (176.1 MHz, CDCl₃): δ 167.8, 144.6 (2C), 142.9, 139.6, 139.3, 135.8, 132.5, 131.5, 130.9, 130.1, 128.8, 128.6 (2C), 128.5 (2C), 128.1, 126.4, 118.7, 35.6. ¹⁹F NMR (658.8 MHz, CDCl₃): δ −144.8 – −145.5 (m, 2F). GC-MS (EI, 70 eV): m/z (%) = 364 (62) [M⁺], 363 (87), 343 (17), 342 (17), 288 (15), 287 (84), 286 (88), 268 (10), 267 (58), 266 (100), 172 (10).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All C-bound H atoms were positioned geometrically (C—H = 0.95 and 0.99 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C). Owing to poor agreement between observed and calculated intensities, one outlier (0 0 2) was omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₂₀H₁₅BF₂N₂S
M_r	364.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.6652 (2), 11.9170 (2), 18.8416 (4)
β (°)	91.7200 (8)
V (Å³)	1720.33 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.27 × 0.15 × 0.04

Data collection
Diffractometer	Bruker D8 QUEST PHOTON-III area detector
Absorption correction	Analytical (SADABS; Krause et al., 2015 )
T_min, T_max	0.702, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	64200, 6292, 5312
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.03
No. of reflections	6292
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.31
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2545790

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026003889/jp2027sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026003889/jp2027Isup2.hkl

checkCIF report

Computing details top

10-(3-Benzylthiophen-2-yl)-5,5-difluoro-5H-4λ⁴,5λ⁴-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine top

Crystal data top

C₂₀H₁₅BF₂N₂S	F(000) = 752
M_r = 364.21	D_x = 1.406 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.6652 (2) Å	Cell parameters from 9889 reflections
b = 11.9170 (2) Å	θ = 2.8–32.5°
c = 18.8416 (4) Å	µ = 0.21 mm⁻¹
β = 91.7200 (8)°	T = 100 K
V = 1720.33 (6) Å³	Plate, colourless
Z = 4	0.27 × 0.15 × 0.04 mm

Data collection top

Bruker D8 QUEST PHOTON-III area detector diffractometer	5312 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.041
φ and ω scans	θ_max = 32.7°, θ_min = 2.8°
Absorption correction: analytical (SADABS; Krause et al., 2015)	h = −11→11
T_min = 0.702, T_max = 0.746	k = −17→18
64200 measured reflections	l = −28→28
6292 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0403P)² + 0.7409P] where P = (F_o² + 2F_c²)/3
6292 reflections	(Δ/σ)_max = 0.001
235 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.30 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
S1	0.84161 (3)	0.77669 (2)	0.66905 (2)	0.01507 (6)
F1	0.37533 (8)	0.47800 (5)	0.87911 (4)	0.02186 (13)
F2	0.44409 (9)	0.62246 (6)	0.95338 (3)	0.02200 (13)
N1	0.42895 (10)	0.65968 (7)	0.82742 (4)	0.01540 (15)
N2	0.67101 (10)	0.54855 (7)	0.88026 (4)	0.01384 (14)
C1	0.28040 (13)	0.71956 (9)	0.81925 (6)	0.02002 (19)
H1	0.191765	0.724323	0.853302	0.024*
C2	0.27586 (13)	0.77380 (9)	0.75314 (6)	0.0224 (2)
H2	0.186268	0.821940	0.735087	0.027*
C3	0.42703 (13)	0.74382 (9)	0.71911 (6)	0.01876 (18)
H3	0.459250	0.766234	0.672925	0.023*
C4	0.52415 (12)	0.67355 (8)	0.76622 (5)	0.01446 (16)
C5	0.69134 (12)	0.62665 (8)	0.76159 (5)	0.01292 (15)
C6	0.76540 (12)	0.56795 (8)	0.81948 (5)	0.01312 (15)
C7	0.93860 (12)	0.53056 (8)	0.83257 (5)	0.01448 (16)
H7	1.031418	0.533229	0.800315	0.017*
C8	0.94721 (13)	0.48929 (8)	0.90137 (5)	0.01685 (17)
H8	1.047172	0.458677	0.925277	0.020*
C9	0.77969 (13)	0.50136 (8)	0.92910 (5)	0.01684 (17)
H9	0.748065	0.479417	0.975450	0.020*
C10	0.79423 (12)	0.64260 (8)	0.69795 (5)	0.01341 (15)
C11	0.86597 (12)	0.56204 (8)	0.65512 (5)	0.01466 (16)
C12	0.96116 (13)	0.61169 (8)	0.59931 (5)	0.01747 (17)
H12	1.019220	0.569191	0.564492	0.021*
C13	0.96074 (13)	0.72614 (9)	0.60079 (5)	0.01759 (17)
H13	1.019433	0.772085	0.567917	0.021*
C14	0.83518 (14)	0.43748 (8)	0.66102 (5)	0.01752 (17)
H14A	0.792936	0.420093	0.708926	0.021*
H14B	0.946934	0.397354	0.655200	0.021*
C15	0.70289 (13)	0.39605 (8)	0.60560 (5)	0.01605 (17)
C16	0.52988 (14)	0.43302 (10)	0.60547 (6)	0.0230 (2)
H16	0.494303	0.484795	0.640544	0.028*
C17	0.40940 (15)	0.39469 (11)	0.55446 (7)	0.0277 (2)
H17	0.292221	0.420597	0.554866	0.033*
C18	0.45901 (16)	0.31889 (11)	0.50298 (7)	0.0277 (2)
H18	0.376319	0.292630	0.468269	0.033*
C19	0.63037 (16)	0.28183 (10)	0.50265 (6)	0.0261 (2)
H19	0.665301	0.229907	0.467558	0.031*
C20	0.75163 (14)	0.32035 (9)	0.55354 (6)	0.01976 (18)
H20	0.868880	0.294677	0.552698	0.024*
B1	0.47484 (14)	0.57533 (9)	0.88759 (6)	0.01587 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01764 (10)	0.01170 (10)	0.01596 (10)	−0.00004 (7)	0.00183 (7)	0.00133 (7)
F1	0.0164 (3)	0.0159 (3)	0.0335 (3)	−0.0049 (2)	0.0042 (2)	−0.0008 (2)
F2	0.0260 (3)	0.0227 (3)	0.0179 (3)	−0.0011 (2)	0.0099 (2)	−0.0029 (2)
N1	0.0126 (3)	0.0151 (3)	0.0186 (4)	−0.0003 (3)	0.0032 (3)	−0.0024 (3)
N2	0.0145 (3)	0.0149 (3)	0.0123 (3)	−0.0024 (3)	0.0025 (3)	−0.0006 (3)
C1	0.0131 (4)	0.0194 (4)	0.0277 (5)	0.0001 (3)	0.0023 (3)	−0.0045 (4)
C2	0.0142 (4)	0.0228 (5)	0.0298 (5)	0.0031 (4)	−0.0031 (4)	−0.0019 (4)
C3	0.0168 (4)	0.0191 (4)	0.0202 (4)	0.0011 (3)	−0.0031 (3)	0.0002 (3)
C4	0.0137 (4)	0.0140 (4)	0.0157 (4)	−0.0001 (3)	0.0010 (3)	−0.0019 (3)
C5	0.0141 (4)	0.0115 (4)	0.0133 (4)	−0.0009 (3)	0.0015 (3)	−0.0012 (3)
C6	0.0133 (3)	0.0137 (4)	0.0125 (3)	−0.0014 (3)	0.0026 (3)	−0.0003 (3)
C7	0.0131 (4)	0.0147 (4)	0.0157 (4)	−0.0009 (3)	0.0006 (3)	−0.0003 (3)
C8	0.0164 (4)	0.0184 (4)	0.0156 (4)	−0.0013 (3)	−0.0020 (3)	0.0010 (3)
C9	0.0188 (4)	0.0185 (4)	0.0132 (4)	−0.0035 (3)	0.0004 (3)	0.0006 (3)
C10	0.0152 (4)	0.0121 (4)	0.0130 (4)	0.0003 (3)	0.0013 (3)	0.0015 (3)
C11	0.0175 (4)	0.0135 (4)	0.0131 (4)	0.0021 (3)	0.0013 (3)	0.0010 (3)
C12	0.0200 (4)	0.0180 (4)	0.0146 (4)	0.0024 (3)	0.0042 (3)	0.0010 (3)
C13	0.0186 (4)	0.0188 (4)	0.0155 (4)	−0.0004 (3)	0.0032 (3)	0.0030 (3)
C14	0.0251 (5)	0.0124 (4)	0.0151 (4)	0.0029 (3)	0.0007 (3)	0.0004 (3)
C15	0.0208 (4)	0.0118 (4)	0.0157 (4)	0.0006 (3)	0.0027 (3)	0.0021 (3)
C16	0.0213 (5)	0.0207 (5)	0.0274 (5)	0.0029 (4)	0.0057 (4)	−0.0007 (4)
C17	0.0184 (5)	0.0273 (5)	0.0373 (6)	−0.0005 (4)	0.0006 (4)	0.0043 (5)
C18	0.0267 (5)	0.0263 (5)	0.0295 (5)	−0.0070 (4)	−0.0058 (4)	0.0023 (4)
C19	0.0308 (5)	0.0226 (5)	0.0248 (5)	−0.0022 (4)	−0.0013 (4)	−0.0066 (4)
C20	0.0225 (4)	0.0164 (4)	0.0204 (4)	0.0015 (3)	0.0014 (4)	−0.0026 (3)
B1	0.0155 (4)	0.0151 (4)	0.0173 (4)	−0.0025 (3)	0.0049 (3)	−0.0021 (3)

Geometric parameters (Å, º) top

S1—C13	1.7093 (10)	C8—H8	0.9500
S1—C10	1.7302 (9)	C9—H9	0.9500
F1—B1	1.3948 (12)	C10—C11	1.3792 (13)
F2—B1	1.3875 (12)	C11—C12	1.4263 (13)
N1—C1	1.3488 (13)	C11—C14	1.5076 (14)
N1—C4	1.3928 (12)	C12—C13	1.3641 (14)
N1—B1	1.5477 (14)	C12—H12	0.9500
N2—C9	1.3457 (12)	C13—H13	0.9500
N2—C6	1.3921 (11)	C14—C15	1.5161 (14)
N2—B1	1.5474 (13)	C14—H14A	0.9900
C1—C2	1.4028 (16)	C14—H14B	0.9900
C1—H1	0.9500	C15—C20	1.3920 (14)
C2—C3	1.3878 (14)	C15—C16	1.3974 (15)
C2—H2	0.9500	C16—C17	1.3900 (17)
C3—C4	1.4155 (14)	C16—H16	0.9500
C3—H3	0.9500	C17—C18	1.3869 (18)
C4—C5	1.4033 (13)	C17—H17	0.9500
C5—C6	1.4015 (13)	C18—C19	1.3860 (18)
C5—C10	1.4672 (12)	C18—H18	0.9500
C6—C7	1.4151 (13)	C19—C20	1.3929 (15)
C7—C8	1.3861 (13)	C19—H19	0.9500
C7—H7	0.9500	C20—H20	0.9500
C8—C9	1.4081 (14)

C13—S1—C10	91.91 (5)	C10—C11—C14	125.18 (9)
C1—N1—C4	107.71 (9)	C12—C11—C14	123.20 (8)
C1—N1—B1	126.85 (8)	C13—C12—C11	113.47 (9)
C4—N1—B1	124.78 (8)	C13—C12—H12	123.3
C9—N2—C6	107.79 (8)	C11—C12—H12	123.3
C9—N2—B1	127.48 (8)	C12—C13—S1	111.67 (7)
C6—N2—B1	124.72 (8)	C12—C13—H13	124.2
N1—C1—C2	110.08 (9)	S1—C13—H13	124.2
N1—C1—H1	125.0	C11—C14—C15	111.89 (8)
C2—C1—H1	125.0	C11—C14—H14A	109.2
C3—C2—C1	107.03 (9)	C15—C14—H14A	109.2
C3—C2—H2	126.5	C11—C14—H14B	109.2
C1—C2—H2	126.5	C15—C14—H14B	109.2
C2—C3—C4	107.05 (9)	H14A—C14—H14B	107.9
C2—C3—H3	126.5	C20—C15—C16	118.54 (10)
C4—C3—H3	126.5	C20—C15—C14	120.55 (9)
N1—C4—C5	120.42 (8)	C16—C15—C14	120.90 (9)
N1—C4—C3	108.10 (8)	C17—C16—C15	120.56 (10)
C5—C4—C3	131.36 (9)	C17—C16—H16	119.7
C6—C5—C4	119.99 (8)	C15—C16—H16	119.7
C6—C5—C10	119.05 (8)	C18—C17—C16	120.48 (11)
C4—C5—C10	120.90 (8)	C18—C17—H17	119.8
N2—C6—C5	120.98 (8)	C16—C17—H17	119.8
N2—C6—C7	108.20 (8)	C19—C18—C17	119.37 (11)
C5—C6—C7	130.45 (8)	C19—C18—H18	120.3
C8—C7—C6	107.02 (8)	C17—C18—H18	120.3
C8—C7—H7	126.5	C18—C19—C20	120.32 (11)
C6—C7—H7	126.5	C18—C19—H19	119.8
C7—C8—C9	107.01 (8)	C20—C19—H19	119.8
C7—C8—H8	126.5	C15—C20—C19	120.73 (10)
C9—C8—H8	126.5	C15—C20—H20	119.6
N2—C9—C8	109.97 (8)	C19—C20—H20	119.6
N2—C9—H9	125.0	F2—B1—F1	109.39 (8)
C8—C9—H9	125.0	F2—B1—N2	110.78 (8)
C11—C10—C5	128.43 (8)	F1—B1—N2	110.35 (8)
C11—C10—S1	111.57 (7)	F2—B1—N1	110.53 (8)
C5—C10—S1	119.99 (7)	F1—B1—N1	110.16 (8)
C10—C11—C12	111.37 (8)	N2—B1—N1	105.59 (7)

C4—N1—C1—C2	−0.25 (12)	C13—S1—C10—C5	178.07 (8)
B1—N1—C1—C2	−171.22 (9)	C5—C10—C11—C12	−178.38 (9)
N1—C1—C2—C3	1.12 (12)	S1—C10—C11—C12	0.69 (11)
C1—C2—C3—C4	−1.50 (12)	C5—C10—C11—C14	7.25 (16)
C1—N1—C4—C5	175.67 (9)	S1—C10—C11—C14	−173.69 (8)
B1—N1—C4—C5	−13.13 (14)	C10—C11—C12—C13	0.24 (13)
C1—N1—C4—C3	−0.70 (11)	C14—C11—C12—C13	174.74 (9)
B1—N1—C4—C3	170.50 (9)	C11—C12—C13—S1	−1.06 (12)
C2—C3—C4—N1	1.38 (11)	C10—S1—C13—C12	1.22 (8)
C2—C3—C4—C5	−174.45 (10)	C10—C11—C14—C15	100.99 (11)
N1—C4—C5—C6	−1.70 (14)	C12—C11—C14—C15	−72.74 (12)
C3—C4—C5—C6	173.70 (10)	C11—C14—C15—C20	116.03 (10)
N1—C4—C5—C10	−178.78 (8)	C11—C14—C15—C16	−63.81 (12)
C3—C4—C5—C10	−3.38 (16)	C20—C15—C16—C17	0.12 (16)
C9—N2—C6—C5	−173.72 (9)	C14—C15—C16—C17	179.97 (10)
B1—N2—C6—C5	7.51 (14)	C15—C16—C17—C18	0.16 (18)
C9—N2—C6—C7	0.03 (10)	C16—C17—C18—C19	−0.21 (19)
B1—N2—C6—C7	−178.74 (8)	C17—C18—C19—C20	−0.01 (18)
C4—C5—C6—N2	4.41 (14)	C16—C15—C20—C19	−0.34 (16)
C10—C5—C6—N2	−178.46 (8)	C14—C15—C20—C19	179.81 (10)
C4—C5—C6—C7	−167.78 (9)	C18—C19—C20—C15	0.29 (18)
C10—C5—C6—C7	9.35 (15)	C9—N2—B1—F2	43.37 (13)
N2—C6—C7—C8	−0.24 (11)	C6—N2—B1—F2	−138.11 (9)
C5—C6—C7—C8	172.72 (10)	C9—N2—B1—F1	−77.93 (12)
C6—C7—C8—C9	0.34 (11)	C6—N2—B1—F1	100.59 (10)
C6—N2—C9—C8	0.19 (11)	C9—N2—B1—N1	163.05 (9)
B1—N2—C9—C8	178.91 (9)	C6—N2—B1—N1	−18.42 (12)
C7—C8—C9—N2	−0.34 (11)	C1—N1—B1—F2	−49.37 (13)
C6—C5—C10—C11	58.94 (14)	C4—N1—B1—F2	141.13 (9)
C4—C5—C10—C11	−123.95 (11)	C1—N1—B1—F1	71.64 (12)
C6—C5—C10—S1	−120.06 (8)	C4—N1—B1—F1	−97.87 (10)
C4—C5—C10—S1	57.05 (11)	C1—N1—B1—N2	−169.22 (9)
C13—S1—C10—C11	−1.09 (8)	C4—N1—B1—N2	21.27 (12)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the S1/C10–C13 and N1/C1–C4 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···F2ⁱ	0.95	2.36	3.2017 (12)	148
C13—H13···F2ⁱⁱ	0.95	2.55	3.3113 (12)	137
C20—H20···F2ⁱⁱⁱ	0.95	2.51	3.3221 (13)	144
C14—H14B···Cg2ⁱⁱⁱ	0.99	2.81	3.5815 (11)	135
C18—H18···Cg1^iv	0.95	2.92	3.7764 (13)	151

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

Summary of short interatomic contacts (Å) top

Contact	Distance	Symmetry operation
H8···F1	2.70	1 + x, y, z
F2···H20	2.51	3/2 - x, 1/2 + y, 3/2 - z
H18···C13	2.87	1 - x, 1 - y, 1 - z
H9···F2	2.36	1 - x, 1 - y, 2 - z
F2···H13	2.55	-1/2 + x, 3/2 - y, 1/2 + z
H1···C17	2.80	1/2 - x, 1/2 + y, 3/2 - z
H9···H8	2.52	2 - x, 1 - y, 2 - z
H19···H13	2.53	2 -x, 1 - y, 1 - z
H8···H19	2.54	1/2 + x, 1/2 - y, 1/2 + z

Acknowledgements

The authors' contributions are as follows; conceptualization MA and GMM; synthesis, ZAP and ASL; X-ray analysis VNK; founding ZAP, NAG and KIH; writing (review and editing of the manuscript) NAG, KIH and MA; supervision MA and GMM.

Funding information

Funding for this research was provided by: the RUDN University (project within the framework of the competition for grant funding of young scientists "Joint start: Making science together"), as well as by Baku Engineering University and Azerbaijan Medical University.

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