Crystal structure and Hirshfeld surface analysis of dimethyl (3aS,6R,6aS,7S)-2-(2,2,2-tri­fluoro­acet­yl)-2,3-di­hydro-1H,6H,7H-3a,6:7,9a-di­epoxy­benzo[de]iso­quinoline-3a1,6a-di­carboxyl­ate

Atioğlu, Z.; Akkurt, M.; Toze, F.A.A.; Dorovatovskii, P.V.; Guliyeva, N.A.; Panahova, H.M.

doi:10.1107/S2056989018014305

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 74| Part 11| November 2018| Pages 1599-1604

https://doi.org/10.1107/S2056989018014305

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Crystal structure and Hirshfeld surface analysis of dimethyl (3aS,6R,6aS,7S)-2-(2,2,2-trifluoroacetyl)-2,3-dihydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline-3a¹,6a-dicarboxylate

Zeliha Atioğlu,^a Mehmet Akkurt,^b Flavien A. A. Toze,^c ^* Pavel V. Dorovatovskii,^d Narmina A. Guliyeva ^e and Humay M. Panahova ^f

^aİlke Education and Health Foundation, Cappadocia University, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cDepartment of Chemistry, Faculty of Sciences, University of Douala, PO Box 24157, Douala, Republic of Cameroon, ^dNational Research Center "Kurchatov Institute", Moscow, Russian Federation, ^eOrganic Chemistry Department, Baku State University, Z. Xalilov Str. 23, Az 1148, Baku, Azerbaijan, and ^fState Economic University of Azerbaijan, Istiqlaliyyat st., 6., AZ1001, Baku, Azerbaijan
^*Correspondence e-mail: toflavien@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 29 August 2018; accepted 10 October 2018; online 19 October 2018)

The title molecule, C₁₈H₁₆F₃NO₇, comprises a fused cyclic system containing four five-membered (two dihydrofuran and two tetrahydrofuran) rings and one six-membered (piperidine) ring. The five-membered dihydrofuran and tetrahydrofuran rings adopt envelope conformations, and the six-membered piperidine ring adopts a distorted chair conformation. Intramolecular O⋯F interactions help to stabilize the conformational arrangement. In the crystal structure, molecules are linked by weak C—H⋯O and C—H⋯F hydrogen bonds, forming a three-dimensional network. The Hirshfeld surface analysis confirms the dominant role of H⋯H contacts in establishing the packing.

Keywords: crystal structure; dihydrofuran ring; tetrahydrofuran ring; fused hexacyclic system; piperidine ring; Hiershfeld surface analysis.

CCDC reference: 1872524

1. Chemical context

Non-covalent interactions, such as hydrogen, aerogen, halogen, chalcogen, pnicogen, tetrel and icosagen bonds, as well as n–π*, π–π stacking, π–cation, π–anion and hydrophobic interactions, have an impact on the synthesis, catalysis and design of materials and on biological processes (Shikhaliyev et al., 2018 ; Hazra et al., 2018 ). These weak forces can also control or organize the aggregation, conformation, tertiary and quaternary structure of a molecule, and its stabilization or other particular properties (Legon, 2017 ; Mahmudov et al., 2017a ,b ). In comparison with well-established hydrogen and halogen bonds (Cavallo et al., 2016 ; Mahmoudi et al., 2018 ; Vandyshev et al., 2017 ), chalcogen, pnicogen, tetrel and icosagen bonds are much less explored (Mahmudov et al., 2017a; Scheiner, 2013 ; Mikherdov et al., 2016 ).

The title compound, C₁₈H₁₆F₃NO₇, has a 7-oxabicyclo[2.2.1]heptene scaffold, thus making it a potential tool for the design and synthesis of new organic materials with various useful properties such as electronic materials, molecular tweezers, etc (Borisova et al., 2018a ,b ). During the structure determination, we noted rather unusual intramolecular O⋯F interactions. Here we report the synthesis, molecular and crystal structure of this compound as well as a Hirshfeld surface analysis.

2. Structural commentary

The molecule of the title compound (Fig. 1) is made up from a fused cyclic system containing four five-membered rings (two dihydrofuran and two tetrahydrofuran) in the usual envelope conformations and a six-membered piperidine ring in a chair conformation. The latter is distorted because the environment of the N1 atom is intermediate between trigonal–planar and trigonal–pyramidal. The puckering parameters of the five-membered dihydrofuran [A (O1/C1/C2/C5/C6), B (O2/C1/C6/C7/C10)] and tetrahydrofuran [C (O1/C2–C5), D (O2/C7–C10)] rings are A: Q(2) = 0.5780 (15) Å, φ(2) = 359.75 (17)°; B: Q(2) = 0.5737 (16) Å, φ(2) = 4.53 (17)°; C: Q(2) = 0.5173 (15) Å, φ(2) = 179.60 (19)°; D: Q(2) = 0.5154 (16) Å, φ(2) = 178.2 (2)°. The puckering parameters of the six-membered piperidine ring (N1/C1/C2/C10–C12) are Q_T = 0.5312 (17) Å, θ = 9.58 (18)°, φ = 329.1 (11)°.

Figure 1
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.

The molecular conformations are stabilized by weak intramolecular C—H⋯O and C—H⋯F interactions (Table 1) between methylene groups (C11; C12) and a methoxy group and the –CF₃ group, respectively. A rather unusual intramolecular O⋯F interaction between one of the oxygen bridgehead atoms (O1) and one of the F atoms of the –CF₃ group [C5—O1⋯F2 = 2.9336 (16) Å; C5—O1⋯F2 = 153.60 (9)°] might help to consolidate the conformational arrangement.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O3ⁱ	0.95	2.44	3.116 (2)	128
C5—H5⋯O2ⁱⁱ	1.00	2.60	3.1960 (19)	118
C7—H7⋯O1ⁱⁱ	1.00	2.54	3.2091 (19)	124
C11—H11B⋯O4	0.99	2.57	3.093 (2)	113
C12—H12A⋯O7ⁱⁱⁱ	0.99	2.52	3.328 (2)	138
C12—H12B⋯O5ⁱⁱⁱ	0.99	2.34	3.030 (2)	127
C12—H12B⋯F1	0.99	2.40	3.043 (2)	122
C12—H12B⋯F2	0.99	2.33	2.962 (2)	121
C16—H16A⋯F3^iv	0.98	2.62	3.475 (2)	146
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

3. Supramolecular features

Intermolecular C—H⋯O interactions involving the O atoms of carbonyl groups, the oxygen bridgehead atoms and methoxy O atoms, as well as C—H⋯F hydrogen bonds define the crystal packing, which is shown in Fig. 2. These packing features lead to the formation of a three-dimensional network structure. C—H⋯π and π–π interactions are not observed, but H⋯H interactions dominate in the packing as detailed in the next section.

Figure 2
The crystal structure of the title compound in a view along [100], emphasizing the intermolecular C—H⋯O and C—H⋯F hydrogen bonds (dashed lines).

4. Hirshfeld surface analysis

Hirshfeld surface and fingerprint plots were generated using CrystalExplorer (McKinnon et al., 2007 ). Hirshfeld surfaces enable the visualization of intermolecular interactions by different colors and color intensity, representing short or long contacts and indicating the relative strength of the interactions. Fig. 3 shows the Hirshfeld surface of the title compound mapped over d_norm where it is evident from the bright-red spots appearing near the oxygen atoms that these atoms play a significant role in the molecular packing. The red spots represent closer contacts and negative d_norm values on the surface, corresponding to the C—H⋯O interactions. The percentage contributions of various contacts to the total Hirshfeld surface are given in Table 2 and are also shown as two-dimensional fingerprint plots in Fig. 4. The H⋯H interactions appear in the middle of the scattered points in the two-dimensional fingerprint plots with an overall contribution to the Hirshfeld surface of 35.6% (Fig. 4b). The contribution from the O⋯H/H⋯O contacts, corresponding to C—H⋯O interactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bonding interaction (28.5%; Fig. 4c). The contribution of the F⋯H/H⋯F intermolecular contacts to the Hirshfeld surfaces is 23.8% (Fig. 4d). The small percentage contributions from the remaining interatomic contacts are summarized in Table 2 and indicated by their fingerprint plots for C⋯H/H⋯C (Fig. 4e), F⋯F (Fig. 4f), F⋯O/O⋯F (Fig. 4g), O⋯O (Fig. 4h), N⋯H/H⋯N (Fig. 4i) and C⋯O/O⋯C (Fig. 4j). The large number of H⋯H, O⋯H/H⋯O and F⋯H/H⋯F interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

Table 2
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound

Contact	Percentage contribution
H⋯H	35.6
O⋯H/H⋯O	28.5
F⋯H/H⋯F	23.8
C⋯H/H⋯C	5.5
F⋯F	2.7
F⋯O/O⋯F	1.6
N⋯H/H⋯N	1.1
O⋯O	1.1
C⋯O/O⋯C	0.2

Figure 3
Hirshfeld surface of the title compound mapped over d_norm.

Figure 4
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) O⋯H/ H⋯O, (d) F⋯H/H⋯F, (e) C⋯H/H⋯C, (f) F⋯F, (g) F⋯O/O⋯F, (h) O⋯O, (i) N⋯H/H⋯N and (j) C⋯O/O⋯C interactions [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

5. Database survey

A search of the Cambridge Structural Database (Version 5.39; Groom et al., 2016 ) for similar structures showed the two closest are those of 2-benzyl-6a,9b-bis(trifluoromethyl)-2,3,6a,9b-tetrahydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline (CSD refcode HENLAQ; Borisova et al., 2018c ) and 2-benzyl-4,5-bis(trifluoromethyl)-2,3,6a,9b-tetrahydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline (HENLEU; Borisova et al., 2018d ). In the crystal of HENLAQ, inversion-related pairs of molecules are linked into dimers by C—H⋯O hydrogen bonds. These dimers form sheets lying parallel to (100). C—H⋯π interactions are also observed in the crystal structure of HENLAQ, together with intramolecular F⋯F contacts. The asymmetric unit of HENLEU contains two molecules. In the crystal, molecules are linked by C—H⋯O and C—H⋯F hydrogen bonds, forming columns along [010]. Likewise, C—H⋯π interactions and F⋯F intramolecular contacts are also present.

6. Synthesis and crystallization

The synthesis of the title compound and its characterization by ¹H NMR, ¹³C NMR, IR and HRMS spectroscopy have previously been reported (Borisova et al., 2018a). Dimethyl acetylenedicarboxylate (DMAD, 1.84 ml, 0.015 mol) was added to a solution of 2,2,2-trifluoro-N,N-bis(furan-2-ylmethyl)acetamide (0.01 mol) in benzene (30 ml). The mixture was heated at reflux for 15.5–40 h at 353 K (GC–MS monitoring until disappearance of the starting material). The reaction mixture was cooled and left overnight at room temperature. The solvent was removed under reduced pressure. The residue (brown oil) was triturated with diethyl ether. The obtained crystals were filtered off and recrystallized from hexane/EtOAc (v:v = 2:1) to give the pure compound as a white powder (2.57 g, 6.2 mmol, yield 62%). R_f = 0.56 (EtOAc/hexane, 2:1, Sorbfil). M.p. 467.2–467.9 K (from hexane/EtOAc). ¹H NMR (400 MHz, CDCl₃): δ 6.74–6.71 (2H, m, H-4 and H-9), 6.46 (2H, dd, J = 2.3 and J = 5.5 Hz, H-5 and H-8), 5.14 (2H, br s, H-6 and H-7), 5.10 (1H, d, J = 14.9 Hz, H-1A), 4.43 (1H, br d, J = 14.9 Hz, H-3A), 4.08 (1H, d, J = 14.9 Hz, H-3B), 3.64 (6H, s, 2 × CO₂Me), 3.59 (1H, d, J = 14.9, H-1B). ¹³C NMR (100 MHz, CDCl₃): δ 170.1 (2 × CO₂Me), 157.2 (q, J = 35.5 Hz, F3C—C), 141.2 (C-5 and C-8), 137.5 (C-4 and C-9), 116.4 (q, J = 288.1 Hz, CF₃), 87.1 (C-3a and C-9a), 83.8 (C-6 and C-7), 71.4 and 68.8 (C-9 and C-6a), 52.4 (2 × CO₂Me), 44.8 (q, J = 3.8 Hz, C-1), 42.4 (C-3). ¹⁹F NMR (282 MHz, CDCl₃): δ −67.7 (s, CF₃). IR ν_max/cm⁻¹ (KBr): 3109, 3055, 2956, 1713, 1688, 1197. HRMS (ESI–TOF): calculated for C₁₈H₁₆F₃NO₇ [M + H]⁺, 415.0879; found, 415.0889.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were fixed and allowed to ride on the parent atoms, with C—H = 0.95–1.00 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for all other H atoms. Eight outliers [(101), (011), ( $[\overline{1}]$ 01), (002), (110), (363), ( $[\overline{3}]$ 03), (111)] were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₈H₁₆F₃NO₇
M_r	415.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	8.7661 (2), 11.2908 (3), 17.5089 (4)
β (°)	96.021 (1)
V (Å³)	1723.41 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.14
Crystal size (mm)	0.35 × 0.32 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.942, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	11170, 3496, 2739
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.091, 1.01
No. of reflections	3496
No. of parameters	264
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1872524

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018014305/wm5463sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018014305/wm5463Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Crystal structure and Hirshfeld surface analysis of dimethyl (3aS,6R,6aS,7S)-2-(2,2,2-trifluoroacetyl)-2,3-dihydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline-3a¹,6a-dicarboxylate, dimethyl (3aS,6R,6aS,7S)-2-(2,2,2-trifluoroacetyl)-2,3-dihydro-1H,6H,7H-3a,6:7,9a-diepoxybenzo[de]isoquinoline-3a¹,6a-dicarboxylate top

Crystal data top

C₁₈H₁₆F₃NO₇	F(000) = 856
M_r = 415.32	D_x = 1.601 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.7661 (2) Å	Cell parameters from 3572 reflections
b = 11.2908 (3) Å	θ = 3.0–25.9°
c = 17.5089 (4) Å	µ = 0.14 mm⁻¹
β = 96.021 (1)°	T = 150 K
V = 1723.41 (7) Å³	Block, colourless
Z = 4	0.35 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	2739 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.028
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.4°, θ_min = 3.1°
T_min = 0.942, T_max = 0.946	h = −10→10
11170 measured reflections	k = −14→11
3496 independent reflections	l = −21→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0391P)² + 0.8462P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3496 reflections	Δρ_max = 0.30 e Å⁻³
264 parameters	Δρ_min = −0.25 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
C1	0.39473 (17)	0.49611 (14)	0.67777 (9)	0.0151 (3)
C2	0.34636 (17)	0.36454 (14)	0.65512 (9)	0.0159 (3)
C3	0.17517 (18)	0.35392 (15)	0.66061 (10)	0.0188 (4)
H3	0.125910	0.313775	0.698918	0.023*
C4	0.10926 (18)	0.41275 (15)	0.60044 (9)	0.0190 (4)
H4	0.002414	0.423058	0.586488	0.023*
C5	0.23948 (17)	0.46040 (14)	0.55824 (9)	0.0166 (3)
H5	0.211134	0.478143	0.502604	0.020*
C6	0.31682 (17)	0.56580 (14)	0.60653 (9)	0.0156 (3)
C7	0.46580 (18)	0.61837 (14)	0.57545 (9)	0.0181 (3)
H7	0.450625	0.648514	0.521478	0.022*
C8	0.53785 (19)	0.70697 (16)	0.63430 (10)	0.0223 (4)
H8	0.534938	0.790901	0.630565	0.027*
C9	0.60537 (19)	0.64310 (16)	0.69172 (10)	0.0215 (4)
H9	0.663054	0.671359	0.737022	0.026*
C10	0.57077 (18)	0.51491 (15)	0.66959 (9)	0.0173 (3)
C11	0.67413 (18)	0.41488 (15)	0.70014 (9)	0.0196 (4)
H11A	0.777907	0.426465	0.683886	0.023*
H11B	0.683028	0.415179	0.756980	0.023*
C12	0.45739 (18)	0.27365 (15)	0.69121 (9)	0.0187 (3)
H12A	0.456518	0.274715	0.747704	0.022*
H12B	0.426248	0.193647	0.672394	0.022*
C13	0.68211 (18)	0.24366 (16)	0.61696 (10)	0.0213 (4)
C14	0.61562 (19)	0.12361 (17)	0.58786 (11)	0.0268 (4)
C15	0.34324 (19)	0.52840 (15)	0.75488 (9)	0.0187 (4)
C16	0.4132 (2)	0.54441 (18)	0.88782 (9)	0.0294 (4)
H16A	0.502378	0.535376	0.926090	0.044*
H16B	0.332265	0.489567	0.899623	0.044*
H16C	0.375106	0.625921	0.888922	0.044*
C17	0.20610 (18)	0.66654 (15)	0.61749 (9)	0.0171 (3)
C18	−0.0373 (2)	0.74427 (17)	0.57152 (12)	0.0332 (5)
H18A	−0.136339	0.716249	0.547019	0.050*
H18B	−0.001422	0.810491	0.541928	0.050*
H18C	−0.048909	0.770680	0.623910	0.050*
N1	0.61226 (15)	0.30034 (12)	0.67137 (8)	0.0174 (3)
O1	0.35051 (12)	0.36756 (10)	0.57348 (6)	0.0157 (2)
O2	0.57083 (12)	0.52159 (10)	0.58756 (6)	0.0171 (3)
O3	0.79898 (15)	0.27623 (13)	0.59189 (8)	0.0386 (4)
O4	0.45760 (13)	0.51821 (11)	0.81186 (6)	0.0234 (3)
O5	0.21495 (14)	0.55547 (12)	0.76498 (7)	0.0274 (3)
O6	0.07292 (13)	0.64922 (10)	0.57403 (7)	0.0226 (3)
O7	0.23490 (14)	0.75410 (11)	0.65517 (7)	0.0263 (3)
F1	0.60895 (14)	0.04589 (10)	0.64497 (7)	0.0422 (3)
F2	0.47566 (12)	0.13074 (10)	0.55061 (6)	0.0350 (3)
F3	0.70476 (14)	0.07621 (12)	0.53923 (8)	0.0509 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0169 (8)	0.0155 (8)	0.0130 (8)	−0.0009 (6)	0.0023 (6)	−0.0006 (6)
C2	0.0181 (8)	0.0163 (8)	0.0139 (8)	−0.0018 (6)	0.0051 (6)	−0.0002 (6)
C3	0.0172 (8)	0.0149 (8)	0.0254 (9)	−0.0042 (6)	0.0082 (7)	−0.0020 (7)
C4	0.0163 (8)	0.0167 (9)	0.0244 (9)	−0.0025 (6)	0.0033 (6)	−0.0048 (7)
C5	0.0173 (8)	0.0169 (8)	0.0153 (8)	0.0008 (6)	0.0002 (6)	−0.0011 (7)
C6	0.0185 (8)	0.0150 (8)	0.0134 (8)	−0.0012 (6)	0.0022 (6)	−0.0005 (6)
C7	0.0199 (8)	0.0168 (9)	0.0179 (8)	−0.0009 (6)	0.0039 (6)	0.0027 (7)
C8	0.0226 (9)	0.0184 (9)	0.0268 (9)	−0.0068 (7)	0.0060 (7)	−0.0007 (7)
C9	0.0213 (8)	0.0222 (9)	0.0205 (9)	−0.0071 (7)	−0.0002 (7)	−0.0038 (7)
C10	0.0191 (8)	0.0184 (9)	0.0144 (8)	−0.0048 (6)	0.0024 (6)	−0.0019 (7)
C11	0.0173 (8)	0.0230 (9)	0.0180 (8)	−0.0029 (7)	−0.0003 (6)	−0.0014 (7)
C12	0.0181 (8)	0.0198 (9)	0.0193 (8)	−0.0011 (7)	0.0064 (6)	0.0027 (7)
C13	0.0171 (8)	0.0241 (10)	0.0225 (9)	0.0007 (7)	0.0020 (7)	−0.0008 (7)
C14	0.0226 (9)	0.0268 (10)	0.0315 (10)	0.0019 (7)	0.0048 (7)	−0.0048 (8)
C15	0.0254 (9)	0.0149 (8)	0.0161 (8)	−0.0005 (7)	0.0042 (7)	0.0006 (7)
C16	0.0470 (11)	0.0304 (11)	0.0114 (8)	0.0037 (9)	0.0057 (8)	−0.0025 (8)
C17	0.0211 (8)	0.0172 (9)	0.0131 (8)	−0.0012 (6)	0.0030 (6)	0.0016 (7)
C18	0.0299 (10)	0.0263 (11)	0.0409 (11)	0.0115 (8)	−0.0074 (8)	−0.0080 (9)
N1	0.0158 (7)	0.0180 (7)	0.0184 (7)	−0.0010 (5)	0.0016 (5)	0.0014 (6)
O1	0.0176 (5)	0.0157 (6)	0.0141 (6)	−0.0001 (4)	0.0034 (4)	−0.0016 (4)
O2	0.0170 (6)	0.0201 (6)	0.0148 (6)	−0.0021 (5)	0.0039 (4)	0.0005 (5)
O3	0.0259 (7)	0.0424 (9)	0.0509 (9)	−0.0105 (6)	0.0205 (6)	−0.0156 (7)
O4	0.0297 (7)	0.0287 (7)	0.0116 (6)	0.0004 (5)	0.0019 (5)	−0.0020 (5)
O5	0.0296 (7)	0.0322 (8)	0.0215 (6)	0.0095 (6)	0.0086 (5)	−0.0015 (5)
O6	0.0212 (6)	0.0194 (6)	0.0261 (6)	0.0044 (5)	−0.0023 (5)	−0.0039 (5)
O7	0.0296 (7)	0.0210 (7)	0.0272 (7)	0.0035 (5)	−0.0020 (5)	−0.0069 (5)
F1	0.0515 (7)	0.0218 (6)	0.0523 (8)	0.0029 (5)	0.0002 (6)	0.0056 (5)
F2	0.0279 (6)	0.0320 (6)	0.0427 (7)	−0.0024 (5)	−0.0073 (5)	−0.0102 (5)
F3	0.0405 (7)	0.0496 (8)	0.0662 (9)	−0.0048 (6)	0.0225 (6)	−0.0341 (7)

Geometric parameters (Å, º) top

C1—C15	1.512 (2)	C11—N1	1.471 (2)
C1—C6	1.569 (2)	C11—H11A	0.9900
C1—C10	1.579 (2)	C11—H11B	0.9900
C1—C2	1.584 (2)	C12—N1	1.467 (2)
C2—O1	1.4341 (19)	C12—H12A	0.9900
C2—C12	1.507 (2)	C12—H12B	0.9900
C2—C3	1.519 (2)	C13—O3	1.213 (2)
C3—C4	1.326 (2)	C13—N1	1.347 (2)
C3—H3	0.9500	C13—C14	1.541 (3)
C4—C5	1.522 (2)	C14—F3	1.327 (2)
C4—H4	0.9500	C14—F2	1.330 (2)
C5—O1	1.4363 (19)	C14—F1	1.336 (2)
C5—C6	1.572 (2)	C15—O5	1.196 (2)
C5—H5	1.0000	C15—O4	1.343 (2)
C6—C17	1.520 (2)	C16—O4	1.455 (2)
C6—C7	1.582 (2)	C16—H16A	0.9800
C7—O2	1.4303 (19)	C16—H16B	0.9800
C7—C8	1.525 (2)	C16—H16C	0.9800
C7—H7	1.0000	C17—O7	1.2006 (19)
C8—C9	1.325 (2)	C17—O6	1.3393 (19)
C8—H8	0.9500	C18—O6	1.441 (2)
C9—C10	1.521 (2)	C18—H18A	0.9800
C9—H9	0.9500	C18—H18B	0.9800
C10—O2	1.4382 (19)	C18—H18C	0.9800
C10—C11	1.510 (2)

C15—C1—C6	116.28 (13)	C9—C10—C1	106.00 (13)
C15—C1—C10	115.76 (13)	N1—C11—C10	110.50 (12)
C6—C1—C10	102.03 (12)	N1—C11—H11A	109.5
C15—C1—C2	110.64 (13)	C10—C11—H11A	109.5
C6—C1—C2	100.86 (12)	N1—C11—H11B	109.5
C10—C1—C2	109.99 (12)	C10—C11—H11B	109.5
O1—C2—C12	110.57 (12)	H11A—C11—H11B	108.1
O1—C2—C3	101.16 (12)	N1—C12—C2	109.50 (13)
C12—C2—C3	121.25 (13)	N1—C12—H12A	109.8
O1—C2—C1	101.14 (11)	C2—C12—H12A	109.8
C12—C2—C1	112.92 (13)	N1—C12—H12B	109.8
C3—C2—C1	107.37 (13)	C2—C12—H12B	109.8
C4—C3—C2	105.15 (14)	H12A—C12—H12B	108.2
C4—C3—H3	127.4	O3—C13—N1	125.15 (16)
C2—C3—H3	127.4	O3—C13—C14	116.83 (15)
C3—C4—C5	106.05 (14)	N1—C13—C14	117.88 (14)
C3—C4—H4	127.0	F3—C14—F2	106.54 (15)
C5—C4—H4	127.0	F3—C14—F1	106.87 (16)
O1—C5—C4	100.37 (12)	F2—C14—F1	107.23 (14)
O1—C5—C6	101.94 (12)	F3—C14—C13	109.82 (14)
C4—C5—C6	108.05 (13)	F2—C14—C13	113.97 (15)
O1—C5—H5	114.9	F1—C14—C13	112.02 (15)
C4—C5—H5	114.9	O5—C15—O4	123.51 (15)
C6—C5—H5	114.9	O5—C15—C1	124.53 (15)
C17—C6—C1	120.34 (13)	O4—C15—C1	111.90 (14)
C17—C6—C5	112.90 (13)	O4—C16—H16A	109.5
C1—C6—C5	100.09 (12)	O4—C16—H16B	109.5
C17—C6—C7	108.88 (13)	H16A—C16—H16B	109.5
C1—C6—C7	98.94 (12)	O4—C16—H16C	109.5
C5—C6—C7	115.09 (13)	H16A—C16—H16C	109.5
O2—C7—C8	100.74 (12)	H16B—C16—H16C	109.5
O2—C7—C6	101.77 (12)	O7—C17—O6	123.57 (15)
C8—C7—C6	108.18 (13)	O7—C17—C6	125.81 (15)
O2—C7—H7	114.8	O6—C17—C6	110.43 (13)
C8—C7—H7	114.8	O6—C18—H18A	109.5
C6—C7—H7	114.8	O6—C18—H18B	109.5
C9—C8—C7	106.02 (15)	H18A—C18—H18B	109.5
C9—C8—H8	127.0	O6—C18—H18C	109.5
C7—C8—H8	127.0	H18A—C18—H18C	109.5
C8—C9—C10	105.27 (14)	H18B—C18—H18C	109.5
C8—C9—H9	127.4	C13—N1—C12	124.77 (14)
C10—C9—H9	127.4	C13—N1—C11	118.78 (13)
O2—C10—C11	109.26 (13)	C12—N1—C11	114.62 (13)
O2—C10—C9	100.58 (13)	C2—O1—C5	96.60 (11)
C11—C10—C9	121.69 (14)	C7—O2—C10	96.93 (11)
O2—C10—C1	101.56 (11)	C15—O4—C16	114.29 (13)
C11—C10—C1	115.03 (13)	C17—O6—C18	116.74 (13)

C15—C1—C2—O1	158.98 (12)	C6—C1—C10—C9	73.08 (14)
C6—C1—C2—O1	35.33 (13)	C2—C1—C10—C9	179.49 (12)
C10—C1—C2—O1	−71.87 (14)	O2—C10—C11—N1	−65.07 (16)
C15—C1—C2—C12	−82.85 (16)	C9—C10—C11—N1	178.56 (14)
C6—C1—C2—C12	153.50 (12)	C1—C10—C11—N1	48.35 (17)
C10—C1—C2—C12	46.30 (16)	O1—C2—C12—N1	57.13 (17)
C15—C1—C2—C3	53.42 (16)	C3—C2—C12—N1	175.15 (14)
C6—C1—C2—C3	−70.24 (14)	C1—C2—C12—N1	−55.37 (17)
C10—C1—C2—C3	−177.43 (13)	O3—C13—C14—F3	0.8 (2)
O1—C2—C3—C4	−32.33 (16)	N1—C13—C14—F3	−175.17 (15)
C12—C2—C3—C4	−154.93 (15)	O3—C13—C14—F2	−118.68 (18)
C1—C2—C3—C4	73.22 (16)	N1—C13—C14—F2	65.4 (2)
C2—C3—C4—C5	−0.44 (17)	O3—C13—C14—F1	119.35 (18)
C3—C4—C5—O1	32.93 (16)	N1—C13—C14—F1	−56.6 (2)
C3—C4—C5—C6	−73.38 (16)	C6—C1—C15—O5	35.8 (2)
C15—C1—C6—C17	4.8 (2)	C10—C1—C15—O5	155.57 (16)
C10—C1—C6—C17	−122.10 (14)	C2—C1—C15—O5	−78.4 (2)
C2—C1—C6—C17	124.52 (14)	C6—C1—C15—O4	−146.90 (14)
C15—C1—C6—C5	−119.37 (14)	C10—C1—C15—O4	−27.14 (19)
C10—C1—C6—C5	113.70 (12)	C2—C1—C15—O4	98.85 (15)
C2—C1—C6—C5	0.31 (13)	C1—C6—C17—O7	58.2 (2)
C15—C1—C6—C7	122.99 (14)	C5—C6—C17—O7	176.13 (15)
C10—C1—C6—C7	−3.95 (14)	C7—C6—C17—O7	−54.7 (2)
C2—C1—C6—C7	−117.33 (12)	C1—C6—C17—O6	−126.65 (15)
O1—C5—C6—C17	−165.16 (12)	C5—C6—C17—O6	−8.77 (18)
C4—C5—C6—C17	−59.95 (17)	C7—C6—C17—O6	120.36 (14)
O1—C5—C6—C1	−35.94 (13)	O3—C13—N1—C12	167.96 (17)
C4—C5—C6—C1	69.27 (14)	C14—C13—N1—C12	−16.5 (2)
O1—C5—C6—C7	68.99 (15)	O3—C13—N1—C11	4.3 (3)
C4—C5—C6—C7	174.20 (13)	C14—C13—N1—C11	179.81 (14)
C17—C6—C7—O2	165.38 (12)	C2—C12—N1—C13	−101.78 (18)
C1—C6—C7—O2	38.92 (14)	C2—C12—N1—C11	62.52 (17)
C5—C6—C7—O2	−66.71 (16)	C10—C11—N1—C13	106.74 (16)
C17—C6—C7—C8	59.79 (16)	C10—C11—N1—C12	−58.57 (17)
C1—C6—C7—C8	−66.68 (15)	C12—C2—O1—C5	−178.88 (12)
C5—C6—C7—C8	−172.31 (13)	C3—C2—O1—C5	51.41 (13)
O2—C7—C8—C9	−31.04 (16)	C1—C2—O1—C5	−59.02 (12)
C6—C7—C8—C9	75.27 (16)	C4—C5—O1—C2	−51.23 (13)
C7—C8—C9—C10	−1.76 (17)	C6—C5—O1—C2	59.90 (13)
C8—C9—C10—O2	33.85 (16)	C8—C7—O2—C10	50.57 (13)
C8—C9—C10—C11	154.49 (15)	C6—C7—O2—C10	−60.77 (13)
C8—C9—C10—C1	−71.55 (16)	C11—C10—O2—C7	179.05 (12)
C15—C1—C10—O2	−158.88 (13)	C9—C10—O2—C7	−51.80 (13)
C6—C1—C10—O2	−31.61 (14)	C1—C10—O2—C7	57.12 (13)
C2—C1—C10—O2	74.81 (14)	O5—C15—O4—C16	−0.7 (2)
C15—C1—C10—C11	83.27 (17)	C1—C15—O4—C16	−178.05 (14)
C6—C1—C10—C11	−149.45 (13)	O7—C17—O6—C18	2.2 (2)
C2—C1—C10—C11	−43.04 (17)	C6—C17—O6—C18	−173.02 (14)
C15—C1—C10—C9	−54.19 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱ	0.95	2.44	3.116 (2)	128
C5—H5···O2ⁱⁱ	1.00	2.60	3.1960 (19)	118
C7—H7···O1ⁱⁱ	1.00	2.54	3.2091 (19)	124
C11—H11B···O4	0.99	2.57	3.093 (2)	113
C12—H12A···O7ⁱⁱⁱ	0.99	2.52	3.328 (2)	138
C12—H12B···O5ⁱⁱⁱ	0.99	2.34	3.030 (2)	127
C12—H12B···F1	0.99	2.40	3.043 (2)	122
C12—H12B···F2	0.99	2.33	2.962 (2)	121
C16—H16A···F3^iv	0.98	2.62	3.475 (2)	146

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

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

Contact	Percentage contribution
H···H	35.6
O···H/H···O	28.5
F···H/H···F	23.8
C···H/H···C	5.5
F···F	2.7
F···O/O···F	1.6
N···H/H···N	1.1
O···O	1.1
C···O/O···C	0.2

Funding information

X-ray crystallographic studies using synchrotron radiation were performed at the scientific facility Kurchatov Synchrotron Radiation Source supported by the Ministry of Education and Science of the Russian Federation (project code RFMEFI61917X0007). This work was partially supported by Baku State University.

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