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Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 2023 Nov 10;79(Pt 12):1132–1136. doi: 10.1107/S2056989023009623

Synthesis, characterization, crystal structure and Hirshfeld surface analysis of isobutyl 4-[4-(di­fluoro­meth­oxy)phen­yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate

Sema Öztürk Yıldırım a,b, Mehmet Akkurt c, Gökalp Çetin d, Rahime Şimşek e, Ray J Butcher f, Ajaya Bhattarai g,*
Editor: S P Kelleyh
PMCID: PMC10833413  PMID: 38313124

In the crystal, the mol­ecules are linked by N—H⋯O and C—H⋯O inter­actions, forming supra­molecular chains parallel to the a axis. These chains pack with C—H⋯π inter­actions between them, forming layers parallel to the (010) plane.

Keywords: crystal structure; 1,4-di­hydro­pyridine ring; cyclo­hexene ring; quinoline ring system; van der Waals inter­actions; Hirshfeld surface analysis

Abstract

In the title compound, C24H29F2NO4, which crystallizes in the ortho­rhom­bic Pca21 space group with Z = 4, the 1,4-di­hydro­pyridine ring adopts a distorted boat conformation, while the cyclo­hexene ring is in a distorted half-chair conformation. In the crystal, the mol­ecules are linked by N—H⋯O and C—H⋯O inter­actions, forming supra­molecular chains parallel to the a axis. These chains pack with C—H⋯π inter­actions between them, forming layers parallel to the (010) plane. The cohesion of the crystal structure is ensured by van der Waals inter­actions between these layers. Hirshfeld surface analysis shows the major contributions to the crystal packing are from H⋯H (56.9%), F⋯H/H⋯F (15.7%), O⋯H/H⋯O (13.7%) and C⋯H/H⋯C (9.5%) contacts.

1. Chemical context

Hexa­hydro­quinoline (HHQ) ring systems occupy a prominent place in medicinal chemistry, attracting the attention of researchers for their versatile structural attributes and pharmacological potential. These ring systems, characterized by a unique combination of pyridine and cyclo­hexane rings, have shown remarkable bioactivity across a spectrum of therapeutic areas. Their capacity to inter­act with specific biological targets has led to the development of HHQ-based compounds with diverse medicinal properties, including anti­microbial, anti-inflammatory, and anti­cancer activities (Ranjbar et al., 2019 ▸). Recent studies have shown that these compounds are effective in cancer-related inflammatory pathways such as TGF-β (Längle et al., 2019 ▸). Additionally, they have been demonstrated to have inhibitory effects on receptors involved in cancer development, such as EGFR, or to reverse multi-drug resistance (Abo Al-Hamd et al., 2023 ▸; Shahraki et al., 2020 ▸).

The choice to synthesize HHQs is also fueled by the accessibility of various synthetic routes and the opportunity to fine-tune their chemical structure to optimize drug-like properties. Multi-component reactions and cyclization strategies provide versatile platforms for their synthesis, allowing for systematic modifications to explore structure–activity relationships (SAR; Batista et al., 2016 ▸). As a result, the strategic pursuit of hexa­hydro­quinoline synthesis continues to be a compelling avenue in medicinal chemistry, promising innovative solutions to pressing medical challenges and drug discovery endeavors. 1.

In this study, isobutyl 4-(4-di­fluoro­meth­oxy­phen­yl)-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carb­oxyl­ate was synthesized and its mol­ecular structure was confirmed by IR, 1H NMR, 13C NMR, HRMS and X-ray crystallography. The inter­molecular inter­actions observed in the crystal packing were investigated by Hirshfeld surface analysis.

2. Structural commentary

The 1,4-di­hydro­pyridine ring (N1/C1/C6–C9) of the title compound (Fig. 1 ▸), which crystallizes in the ortho­rhom­bic Pca21 space group with Z = 4, adopts a distorted boat conformation [puckering parameters (Cremer & Pople, 1975 ▸) are Q T = 0.2779 (16) Å, θ = 73.7 (3)° and φ = 179.1 (3)°], while the cyclo­hexene ring (C1–C6) has a distorted half-chair conformation [puckering parameters are Q T = 0.4464 (18) Å, θ = 48.9 (2)° and φ = 126.3 (3)°]. The 4-(4-di­fluoro­meth­oxy­phenyl) ring (C18–C23) makes a dihedral angle of 88.73 (6)° with the mean plane of the quinoline ring system [N1/C1–C9; maximum deviation = 0.415 (2) Å for C3]. The geometrical parameters of the title compound are in agreement with those reported for similar compounds in the Database survey section.

Figure 1.

Figure 1

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View of the title mol­ecule. Displacement ellipsoids are drawn at the 30% probability level.

3. Supra­molecular features and Hirshfeld surface analysis

In the crystal, the mol­ecules are linked by N—H⋯O and C—H⋯O inter­actions, forming supra­molecular chains parallel to the a-axis direction (see Table 1 ▸; Figs. 2 ▸ and 3 ▸). These chains pack with C—H⋯π inter­actions between them, forming layers parallel to the (010) plane (Fig. 4 ▸). The cohesion of the crystal structure is ensured by van der Waals inter­actions between these layers.

Table 1. Hydrogen-bond geometry (Å, °).

Cg3 is the centroid the benzene ring of the 4-(4-di­fluoro­meth­oxy­phenyl group of the title compound.

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1N⋯O1i 0.87 (2) 1.98 (2) 2.8426 (17) 173 (2)
C19—H19A⋯O2i 0.95 2.43 3.100 (2) 127
C3—H3A⋯Cg3ii 0.99 2.84 3.7345 (18) 151
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Symmetry codes: (i) Inline graphic ; (ii) Inline graphic .

Figure 2.

Figure 2

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A view of the mol­ecular packing of the title compound along the a-axis with the N—H⋯O, C—H⋯O hydrogen bonds and C—H⋯π inter­actions shown as dashed lines.

Figure 3.

Figure 3

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View of the mol­ecular packing along the b-axis. Hydrogen bonds are shown as dashed lines.

Figure 4.

Figure 4

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View of the mol­ecular packing along the c-axis. Hydrogen bonds are shown as dashed lines.

The Hirshfeld surfaces and their corresponding two-dimensional fingerprint plots were calculated using the software package Crystal Explorer 17.5 (Spackman et al., 2021 ▸). The d norm surfaces are mapped over a fixed color scale from −0.5961 (red) to 1.9017 (blue) a.u. Red spots on the surface correspond to O⋯H/H⋯O inter­actions (Tables 1 ▸ and 2 ▸; Fig. 5 ▸ a,b).

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

H15A⋯H10B 2.37 1 − x, 1 − y, − Inline graphic  + z
F2⋯H11B 2.83 Inline graphic  − x, y, − Inline graphic  + z
O1⋯H1N 1.98 Inline graphic  + x, 1 − y, z
H10A⋯H22A 2.47 Inline graphic  − x, y, Inline graphic  + z
H17B⋯H22A 2.58 x, −1 + y, z
H12A⋯H17C 2.54 − Inline graphic  + x, −y, z
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Figure 5.

Figure 5

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(a) Front and (b) back views of the three-dimensional Hirshfeld surface for the title compound.

In Fig. 6 ▸, fingerprint plots of the most important non-covalent inter­actions for the title compound are shown. The major contributions to the crystal packing are from H⋯H (56.9%), F⋯H/H⋯F (15.7%), O⋯H/H⋯O (13.7%) and C⋯H/H⋯C (9.5%) contacts. O⋯C/C⋯O (1.1%), F⋯C/C⋯F (1.0%), C⋯C (0.7%), F⋯O/O⋯F (0.6%), O⋯N/N⋯O (0.5%) and N⋯H/H⋯N (0.2%) contacts, which contribute less than 1.1%, are not shown in Fig.7.

Figure 6.

Figure 6

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The two-dimensional fingerprint plots for the title compound showing (a) all inter­actions, and delineated into (b) H⋯H, (c) F⋯H/H⋯F, (d) O⋯H/H⋯O and (e) C⋯H/H⋯C 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 of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ▸) for similar structures with the 1,4,5,6,7,8-hexa­hydro­quinoline group showed that the nine most closely related to the title compound are LIMYUF (Pehlivanlar et al., 2023 ▸), WEZJUK (Yıldırım et al., 2023 ▸), ECUCUE (Yıldırım et al., 2022 ▸), LOQCAX (Steiger et al., 2014 ▸), NEQMON (Öztürk Yildirim, et al., 2013 ▸), PECPUK (Gündüz et al., 2012 ▸), IMEJOA (Linden et al., 2011 ▸), PUGCIE (Mookiah et al., 2009 ▸), UCOLOO (Linden et al., 2006 ▸) and DAYJET (Linden et al., 2005 ▸). In all of these compounds, mol­ecules are linked by N—H⋯O hydrogen bonds. Furthermore, C—H⋯F hydrogen bonds in LIMYUF, C—H⋯O hydrogen bonds in WEZJUK, ECUCUE, NEQMON, IMEJOA and PUGCIE and C—H⋯π inter­actions in LIMYUF, WEZJUK and ECUCUE were also observed.

5. Synthesis and crystallization

The synthesis of the compound was carried out by refluxing 1 mmol of 4-(4-di­fluoro­meth­oxy)benzaldehyde, isobutyl aceto­acetate, 4,4-methyl-1,3-cyclo­hexa­ndione and 5 mmol of ammonium acetate in methanol. The reaction process was monitored by thin-layer chromatography [ethyl acetate-n-hexane (1:1)], and after the reaction was complete, the mixture was allowed to stand at room temperature for a while and then poured into an ice–water mixture (Fig. 7 ▸). The resulting precipitates were purified again by crystallization with methanol (Yıldırım et al., 2023 ▸).

Figure 7.

Figure 7

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Synthetic scheme.

Isobutyl 4-(4-di­fluoro­meth­oxy­phen­yl)-2,6,6-tri­methyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carbox­y­l­ate

Light-yellow solid, m.p: 489–491 K, yield: 85%. IR (cm−1) 3291 (N—H), 1674 (C=O, ester), 1597 (C=O, ketone). 1H NMR (400 MHz, DMSO-d 6): δ 0.69 [3H, d, J = 9 Hz, –CH(CH3 )a], 0.77 [3H, d, J = 9 Hz, –CH(CH3 )b], 0.81 (3H, s, 6-CH3), 0.97 (3H, s, 6-CH3), 1.52–1.65 (2H, m, quinoline H7), 1.72–1.81 (H, m, –CH–), 2.26 (3H, s, 2-CH3), 2.46–2.50 (2H, m, quinoline H8), 3.63–3.72 (2H, m, –CH2 )–, 4.94 (H, s, quinoline H4), 6.96 (2H, dd, J = 9.2, 6.8 Hz, Ar-H3,5), 7.16 (2H, dd, J = 9.2, 6.8 Hz, Ar-H4,6), 7.26 (H, s, OCHF2), 9.02 (H, s, NH). 13C NMR (100 MHz, DMSO-d 6): 18.6 (2-CH3), 22.3 [–CH(CH3 ) a ], 22.9 [–CH(CH3 ) b ], 23.4 (C-8), 24.2 (6-CH3), 24.8 (6-CH3), 33.5 (C-7), 34.1 (C-4), 35 (–CH–), 39.5 (C-6), 68.2 (–CH2–), 103.8 (C-3), 108.4 (C-4a), 114.2, 116.7, 125.4, 128.2, 135.5, 157.4 (phenyl carbons), 147.1(C-2), 150.6 (C-8a), 166.9 (–COO–), 168.3 (OCHF2) 199.6 (C-5). HRMS (ESI/Q-TOF) m/z: [M + H]+ calculated for C23H25F4NO3: 420.1942; found: 420.2150.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The N-bound H atom was located in a difference-Fourier map and refined freely [N1—H1N = 0.87 (2) Å]. All C-bound H atoms were positioned geometrically [C—H = 0.95–1.00 Å] and refined using a riding model with U iso(H) = 1.2 or 1.5U eq(C).

Table 3. Experimental details.

Crystal data
Chemical formula C24H29F2NO4
M r 433.48
Crystal system, space group Orthorhombic, P c a21
Temperature (K) 100
a, b, c (Å) 11.9879 (7), 12.1807 (7), 15.4518 (9)
V (Å3) 2256.3 (2)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.10
Crystal size (mm) 0.27 × 0.24 × 0.16
 
Data collection
Diffractometer Bruker Quest D8 with Photon 2 detector
Absorption correction Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max 0.718, 0.744
No. of measured, independent and observed [I > 2σ(I)] reflections 103269, 9491, 7264
R int 0.080
(sin θ/λ)max (Å−1) 0.826
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.045, 0.107, 1.03
No. of reflections 9491
No. of parameters 289
No. of restraints 1
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.32, −0.29
Absolute structure Flack x determined using 2721 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter 0.0 (2)
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Computer programs: APEX2 and SAINT (Bruker, 2018 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2020 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023009623/ev2001sup1.cif

e-79-01132-sup1.cif (3MB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023009623/ev2001Isup2.hkl

e-79-01132-Isup2.hkl (753.3KB, hkl)
Click here for additional data file. (8.9KB, cml)

Supporting information file. DOI: 10.1107/S2056989023009623/ev2001Isup3.cml

CCDC reference: 2305562

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

Authors’ contributions are as follows. Conceptualization, RS and SÖY; methodology, RS and GÇ; investigation, RS and SÖY; writing (original draft), GÇ and MA; writing (review and editing of the manuscript), RS and SÖY; crystal data production and validation, RJB and SÖY; visualization, MA; funding acquisition, RJB; resources, AB, RJB and RS.

supplementary crystallographic information

Crystal data

C24H29F2NO4 Dx = 1.276 Mg m−3
Mr = 433.48 Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21 Cell parameters from 9859 reflections
a = 11.9879 (7) Å θ = 2.4–32.7°
b = 12.1807 (7) Å µ = 0.10 mm−1
c = 15.4518 (9) Å T = 100 K
V = 2256.3 (2) Å3 Chunk, light yellow
Z = 4 0.27 × 0.24 × 0.16 mm
F(000) = 920
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Data collection

Bruker Quest D8 with Photon 2 detector diffractometer 7264 reflections with I > 2σ(I)
φ and ω scans Rint = 0.080
Absorption correction: multi-scan (SADABS; Krause et al., 2015) θmax = 36.0°, θmin = 2.4°
Tmin = 0.718, Tmax = 0.744 h = −18→19
103269 measured reflections k = −20→19
9491 independent reflections l = −25→21
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Refinement

Refinement on F2 Hydrogen site location: mixed
Least-squares matrix: full H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.045 w = 1/[σ2(Fo2) + (0.0508P)2 + 0.3823P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.107 (Δ/σ)max < 0.001
S = 1.03 Δρmax = 0.32 e Å−3
9491 reflections Δρmin = −0.29 e Å−3
289 parameters Absolute structure: Flack x determined using 2721 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint Absolute structure parameter: 0.0 (2)
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Special details

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

x y z Uiso*/Ueq
F1 0.49509 (14) 0.92511 (11) 0.20621 (10) 0.0455 (4)
F2 0.36176 (12) 0.80630 (13) 0.21602 (10) 0.0467 (4)
O1 0.65307 (10) 0.66738 (10) 0.65205 (8) 0.0198 (2)
O2 0.72200 (10) 0.33422 (10) 0.48402 (9) 0.0239 (3)
O3 0.60039 (10) 0.19451 (9) 0.48360 (8) 0.0184 (2)
O4 0.53670 (11) 0.76006 (11) 0.24983 (8) 0.0236 (3)
N1 0.36644 (10) 0.41080 (11) 0.60065 (9) 0.0143 (2)
H1N 0.299 (2) 0.3886 (19) 0.6122 (14) 0.019 (5)*
C1 0.40589 (12) 0.50413 (12) 0.63969 (10) 0.0128 (3)
C2 0.32686 (12) 0.56285 (13) 0.69932 (10) 0.0149 (3)
H2A 0.279873 0.508580 0.730076 0.018*
H2B 0.277189 0.611193 0.665143 0.018*
C3 0.39163 (14) 0.63141 (13) 0.76504 (11) 0.0171 (3)
H3A 0.429018 0.581636 0.806558 0.021*
H3B 0.338594 0.677625 0.797973 0.021*
C4 0.47947 (13) 0.70546 (13) 0.72264 (11) 0.0165 (3)
C5 0.55598 (12) 0.63711 (12) 0.66451 (10) 0.0142 (3)
C6 0.51077 (12) 0.54097 (12) 0.62178 (10) 0.0134 (3)
C7 0.57801 (12) 0.48870 (12) 0.54998 (10) 0.0129 (2)
H7A 0.658250 0.488219 0.567679 0.015*
C8 0.54078 (12) 0.37018 (12) 0.53589 (10) 0.0135 (3)
C9 0.43551 (13) 0.33826 (12) 0.55678 (10) 0.0142 (3)
C10 0.54927 (15) 0.76147 (18) 0.79303 (13) 0.0285 (4)
H10A 0.584192 0.705497 0.829657 0.043*
H10B 0.500970 0.808215 0.828535 0.043*
H10C 0.607286 0.806523 0.765913 0.043*
C11 0.42455 (16) 0.79274 (14) 0.66419 (14) 0.0246 (4)
H11A 0.482159 0.841376 0.640633 0.037*
H11B 0.371361 0.835939 0.698245 0.037*
H11C 0.385240 0.756348 0.616550 0.037*
C12 0.37972 (13) 0.22972 (13) 0.53973 (11) 0.0186 (3)
H12A 0.400712 0.203315 0.482072 0.028*
H12B 0.298580 0.238862 0.542595 0.028*
H12C 0.403522 0.176294 0.583404 0.028*
C13 0.62870 (13) 0.30006 (12) 0.49936 (10) 0.0150 (3)
C14 0.68925 (15) 0.12977 (14) 0.44523 (12) 0.0208 (3)
H14A 0.751816 0.122384 0.486642 0.025*
H14B 0.717478 0.166562 0.392459 0.025*
C15 0.64362 (16) 0.01733 (14) 0.42246 (14) 0.0260 (4)
H15A 0.576642 0.027434 0.384717 0.031*
C16 0.6088 (3) −0.04712 (19) 0.5015 (2) 0.0529 (8)
H16A 0.544199 −0.011657 0.528503 0.079*
H16B 0.670705 −0.049424 0.542902 0.079*
H16C 0.588934 −0.122088 0.484414 0.079*
C17 0.7331 (2) −0.04286 (16) 0.37018 (15) 0.0330 (4)
H17A 0.747606 −0.002683 0.316403 0.050*
H17B 0.706990 −0.117084 0.356413 0.050*
H17C 0.801872 −0.047357 0.404232 0.050*
C18 0.56699 (12) 0.55695 (12) 0.46724 (10) 0.0137 (3)
C19 0.46204 (13) 0.59010 (14) 0.43930 (11) 0.0184 (3)
H19A 0.398046 0.567489 0.470878 0.022*
C20 0.44827 (14) 0.65559 (15) 0.36621 (12) 0.0208 (3)
H20A 0.375930 0.676416 0.347231 0.025*
C21 0.54288 (14) 0.68982 (13) 0.32165 (11) 0.0183 (3)
C22 0.64869 (13) 0.65619 (13) 0.34636 (11) 0.0175 (3)
H22A 0.712375 0.678221 0.314155 0.021*
C23 0.66020 (13) 0.58949 (13) 0.41925 (11) 0.0159 (3)
H23A 0.732370 0.565862 0.436503 0.019*
C24 0.45780 (18) 0.84020 (16) 0.25354 (14) 0.0294 (4)
H24A 0.444326 0.863192 0.314777 0.035*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
F1 0.0608 (9) 0.0302 (6) 0.0454 (8) 0.0086 (6) 0.0104 (7) 0.0181 (6)
F2 0.0317 (7) 0.0612 (9) 0.0474 (8) 0.0089 (6) −0.0074 (6) 0.0154 (7)
O1 0.0120 (5) 0.0199 (5) 0.0276 (6) −0.0016 (4) 0.0042 (4) −0.0068 (5)
O2 0.0134 (5) 0.0212 (5) 0.0371 (7) −0.0005 (4) 0.0070 (5) −0.0075 (5)
O3 0.0158 (5) 0.0142 (5) 0.0252 (6) 0.0018 (4) 0.0030 (4) −0.0036 (4)
O4 0.0262 (6) 0.0255 (6) 0.0191 (6) 0.0043 (5) 0.0044 (5) 0.0068 (5)
N1 0.0093 (5) 0.0162 (6) 0.0173 (6) −0.0009 (4) 0.0014 (5) −0.0004 (5)
C1 0.0110 (6) 0.0149 (6) 0.0124 (6) 0.0015 (5) 0.0006 (5) 0.0011 (5)
C2 0.0116 (6) 0.0179 (6) 0.0153 (7) 0.0009 (5) 0.0033 (5) −0.0012 (5)
C3 0.0151 (7) 0.0203 (7) 0.0158 (7) −0.0002 (6) 0.0034 (5) −0.0026 (6)
C4 0.0129 (6) 0.0187 (7) 0.0177 (7) −0.0003 (5) 0.0031 (5) −0.0051 (5)
C5 0.0122 (7) 0.0156 (6) 0.0148 (6) 0.0015 (5) 0.0004 (5) −0.0007 (5)
C6 0.0113 (6) 0.0143 (6) 0.0145 (6) 0.0004 (5) 0.0005 (5) −0.0005 (5)
C7 0.0095 (6) 0.0147 (6) 0.0145 (6) 0.0001 (5) 0.0017 (5) −0.0013 (5)
C8 0.0110 (6) 0.0141 (6) 0.0154 (6) 0.0006 (5) 0.0009 (5) −0.0011 (5)
C9 0.0130 (6) 0.0151 (6) 0.0146 (7) 0.0004 (5) −0.0001 (5) 0.0012 (5)
C10 0.0201 (8) 0.0368 (10) 0.0285 (9) −0.0063 (7) 0.0049 (7) −0.0175 (8)
C11 0.0202 (8) 0.0184 (7) 0.0353 (10) 0.0029 (6) 0.0080 (7) 0.0023 (7)
C12 0.0159 (7) 0.0172 (7) 0.0229 (8) −0.0034 (5) 0.0021 (6) −0.0016 (6)
C13 0.0141 (6) 0.0153 (6) 0.0156 (7) 0.0010 (5) −0.0002 (5) −0.0020 (5)
C14 0.0185 (7) 0.0177 (7) 0.0261 (8) 0.0051 (6) 0.0032 (6) −0.0039 (6)
C15 0.0286 (9) 0.0163 (7) 0.0331 (10) 0.0030 (6) 0.0065 (7) −0.0029 (7)
C16 0.0751 (19) 0.0233 (10) 0.0603 (17) 0.0074 (11) 0.0366 (15) 0.0097 (10)
C17 0.0388 (11) 0.0202 (8) 0.0401 (11) 0.0047 (7) 0.0097 (9) −0.0055 (8)
C18 0.0115 (6) 0.0139 (6) 0.0157 (7) −0.0003 (5) 0.0021 (5) −0.0013 (5)
C19 0.0124 (6) 0.0234 (7) 0.0195 (7) 0.0007 (6) 0.0024 (5) 0.0035 (6)
C20 0.0144 (7) 0.0279 (8) 0.0201 (8) 0.0024 (6) 0.0000 (6) 0.0044 (7)
C21 0.0202 (7) 0.0183 (7) 0.0164 (7) 0.0010 (6) 0.0036 (6) 0.0019 (6)
C22 0.0160 (7) 0.0176 (7) 0.0190 (7) −0.0020 (5) 0.0049 (6) −0.0007 (6)
C23 0.0118 (6) 0.0160 (6) 0.0200 (7) −0.0013 (5) 0.0023 (5) −0.0015 (5)
C24 0.0336 (10) 0.0265 (9) 0.0280 (10) 0.0059 (7) 0.0031 (8) 0.0076 (7)
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Geometric parameters (Å, º)

F1—C24 1.343 (2) C10—H10B 0.9800
F2—C24 1.354 (3) C10—H10C 0.9800
O1—C5 1.2361 (19) C11—H11A 0.9800
O2—C13 1.2166 (19) C11—H11B 0.9800
O3—C13 1.3518 (18) C11—H11C 0.9800
O3—C14 1.4520 (19) C12—H12A 0.9800
O4—C24 1.360 (2) C12—H12B 0.9800
O4—C21 1.403 (2) C12—H12C 0.9800
N1—C1 1.371 (2) C14—C15 1.516 (2)
N1—C9 1.388 (2) C14—H14A 0.9900
N1—H1N 0.87 (2) C14—H14B 0.9900
C1—C6 1.363 (2) C15—C16 1.511 (3)
C1—C2 1.503 (2) C15—C17 1.530 (3)
C2—C3 1.527 (2) C15—H15A 1.0000
C2—H2A 0.9900 C16—H16A 0.9800
C2—H2B 0.9900 C16—H16B 0.9800
C3—C4 1.533 (2) C16—H16C 0.9800
C3—H3A 0.9900 C17—H17A 0.9800
C3—H3B 0.9900 C17—H17B 0.9800
C4—C5 1.530 (2) C17—H17C 0.9800
C4—C10 1.532 (2) C18—C19 1.390 (2)
C4—C11 1.543 (2) C18—C23 1.398 (2)
C5—C6 1.449 (2) C19—C20 1.392 (2)
C6—C7 1.512 (2) C19—H19A 0.9500
C7—C8 1.527 (2) C20—C21 1.391 (2)
C7—C18 1.531 (2) C20—H20A 0.9500
C7—H7A 1.0000 C21—C22 1.386 (2)
C8—C9 1.359 (2) C22—C23 1.396 (2)
C8—C13 1.469 (2) C22—H22A 0.9500
C9—C12 1.505 (2) C23—H23A 0.9500
C10—H10A 0.9800 C24—H24A 1.0000
C13—O3—C14 113.95 (12) C9—C12—H12B 109.5
C24—O4—C21 116.16 (14) H12A—C12—H12B 109.5
C1—N1—C9 122.48 (13) C9—C12—H12C 109.5
C1—N1—H1N 119.2 (15) H12A—C12—H12C 109.5
C9—N1—H1N 117.1 (15) H12B—C12—H12C 109.5
C6—C1—N1 120.11 (14) O2—C13—O3 121.40 (14)
C6—C1—C2 123.32 (14) O2—C13—C8 122.38 (14)
N1—C1—C2 116.55 (13) O3—C13—C8 116.23 (13)
C1—C2—C3 110.33 (12) O3—C14—C15 108.70 (14)
C1—C2—H2A 109.6 O3—C14—H14A 109.9
C3—C2—H2A 109.6 C15—C14—H14A 109.9
C1—C2—H2B 109.6 O3—C14—H14B 109.9
C3—C2—H2B 109.6 C15—C14—H14B 109.9
H2A—C2—H2B 108.1 H14A—C14—H14B 108.3
C2—C3—C4 112.76 (13) C16—C15—C14 112.43 (19)
C2—C3—H3A 109.0 C16—C15—C17 111.82 (17)
C4—C3—H3A 109.0 C14—C15—C17 107.61 (16)
C2—C3—H3B 109.0 C16—C15—H15A 108.3
C4—C3—H3B 109.0 C14—C15—H15A 108.3
H3A—C3—H3B 107.8 C17—C15—H15A 108.3
C5—C4—C10 109.37 (13) C15—C16—H16A 109.5
C5—C4—C3 110.02 (13) C15—C16—H16B 109.5
C10—C4—C3 109.49 (14) H16A—C16—H16B 109.5
C5—C4—C11 106.68 (13) C15—C16—H16C 109.5
C10—C4—C11 109.99 (15) H16A—C16—H16C 109.5
C3—C4—C11 111.25 (13) H16B—C16—H16C 109.5
O1—C5—C6 121.47 (14) C15—C17—H17A 109.5
O1—C5—C4 119.58 (14) C15—C17—H17B 109.5
C6—C5—C4 118.88 (13) H17A—C17—H17B 109.5
C1—C6—C5 121.21 (14) C15—C17—H17C 109.5
C1—C6—C7 120.13 (14) H17A—C17—H17C 109.5
C5—C6—C7 118.37 (13) H17B—C17—H17C 109.5
C6—C7—C8 110.30 (12) C19—C18—C23 118.43 (15)
C6—C7—C18 109.76 (12) C19—C18—C7 119.69 (13)
C8—C7—C18 111.67 (12) C23—C18—C7 121.86 (13)
C6—C7—H7A 108.3 C18—C19—C20 121.71 (15)
C8—C7—H7A 108.3 C18—C19—H19A 119.1
C18—C7—H7A 108.3 C20—C19—H19A 119.1
C9—C8—C13 126.22 (14) C21—C20—C19 118.47 (15)
C9—C8—C7 120.53 (13) C21—C20—H20A 120.8
C13—C8—C7 113.25 (12) C19—C20—H20A 120.8
C8—C9—N1 119.20 (14) C22—C21—C20 121.41 (15)
C8—C9—C12 128.48 (14) C22—C21—O4 116.50 (14)
N1—C9—C12 112.32 (13) C20—C21—O4 122.09 (15)
C4—C10—H10A 109.5 C21—C22—C23 118.99 (15)
C4—C10—H10B 109.5 C21—C22—H22A 120.5
H10A—C10—H10B 109.5 C23—C22—H22A 120.5
C4—C10—H10C 109.5 C22—C23—C18 120.93 (15)
H10A—C10—H10C 109.5 C22—C23—H23A 119.5
H10B—C10—H10C 109.5 C18—C23—H23A 119.5
C4—C11—H11A 109.5 F1—C24—F2 106.55 (17)
C4—C11—H11B 109.5 F1—C24—O4 107.35 (17)
H11A—C11—H11B 109.5 F2—C24—O4 110.76 (17)
C4—C11—H11C 109.5 F1—C24—H24A 110.7
H11A—C11—H11C 109.5 F2—C24—H24A 110.7
H11B—C11—H11C 109.5 O4—C24—H24A 110.7
C9—C12—H12A 109.5
C9—N1—C1—C6 13.6 (2) C13—C8—C9—C12 −7.0 (3)
C9—N1—C1—C2 −168.22 (14) C7—C8—C9—C12 173.21 (15)
C6—C1—C2—C3 −25.9 (2) C1—N1—C9—C8 −13.9 (2)
N1—C1—C2—C3 155.98 (14) C1—N1—C9—C12 165.30 (14)
C1—C2—C3—C4 50.56 (18) C14—O3—C13—O2 −1.8 (2)
C2—C3—C4—C5 −53.48 (18) C14—O3—C13—C8 178.30 (14)
C2—C3—C4—C10 −173.70 (14) C9—C8—C13—O2 −178.39 (17)
C2—C3—C4—C11 64.52 (17) C7—C8—C13—O2 1.4 (2)
C10—C4—C5—O1 −31.4 (2) C9—C8—C13—O3 1.5 (2)
C3—C4—C5—O1 −151.72 (15) C7—C8—C13—O3 −178.68 (13)
C11—C4—C5—O1 87.49 (18) C13—O3—C14—C15 −174.28 (15)
C10—C4—C5—C6 151.64 (15) O3—C14—C15—C16 −64.8 (2)
C3—C4—C5—C6 31.3 (2) O3—C14—C15—C17 171.65 (16)
C11—C4—C5—C6 −89.44 (17) C6—C7—C18—C19 −48.25 (19)
N1—C1—C6—C5 −177.73 (14) C8—C7—C18—C19 74.40 (18)
C2—C1—C6—C5 4.2 (2) C6—C7—C18—C23 130.33 (15)
N1—C1—C6—C7 8.5 (2) C8—C7—C18—C23 −107.02 (16)
C2—C1—C6—C7 −169.55 (14) C23—C18—C19—C20 −1.0 (2)
O1—C5—C6—C1 176.01 (15) C7—C18—C19—C20 177.62 (15)
C4—C5—C6—C1 −7.1 (2) C18—C19—C20—C21 −1.3 (3)
O1—C5—C6—C7 −10.1 (2) C19—C20—C21—C22 2.8 (3)
C4—C5—C6—C7 166.76 (14) C19—C20—C21—O4 −176.98 (16)
C1—C6—C7—C8 −26.47 (19) C24—O4—C21—C22 −142.79 (17)
C5—C6—C7—C8 159.58 (13) C24—O4—C21—C20 37.0 (2)
C1—C6—C7—C18 96.98 (16) C20—C21—C22—C23 −2.1 (3)
C5—C6—C7—C18 −76.97 (17) O4—C21—C22—C23 177.71 (14)
C6—C7—C8—C9 26.2 (2) C21—C22—C23—C18 −0.2 (2)
C18—C7—C8—C9 −96.17 (17) C19—C18—C23—C22 1.8 (2)
C6—C7—C8—C13 −153.64 (13) C7—C18—C23—C22 −176.84 (14)
C18—C7—C8—C13 84.02 (15) C21—O4—C24—F1 151.23 (16)
C13—C8—C9—N1 172.06 (15) C21—O4—C24—F2 −92.82 (19)
C7—C8—C9—N1 −7.7 (2)
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Hydrogen-bond geometry (Å, º)

Cg3 is the centroid the benzene ring of the 4-(4-difluoromethoxyphenyl group of the title compound.

D—H···A D—H H···A D···A D—H···A
N1—H1N···O1i 0.87 (2) 1.98 (2) 2.8426 (17) 173 (2)
C12—H12A···O3 0.98 2.40 2.817 (2) 105
C19—H19A···O2i 0.95 2.43 3.100 (2) 127
C3—H3A···Cg3ii 0.99 2.84 3.7345 (18) 151
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Symmetry codes: (i) x−1/2, −y+1, z; (ii) −x+1, −y+1, z+1/2.

References

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023009623/ev2001sup1.cif

e-79-01132-sup1.cif (3MB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023009623/ev2001Isup2.hkl

e-79-01132-Isup2.hkl (753.3KB, hkl)
Click here for additional data file. (8.9KB, cml)

Supporting information file. DOI: 10.1107/S2056989023009623/ev2001Isup3.cml

CCDC reference: 2305562

Additional supporting information: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography

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