research communications
Synthesis, tert-butyl 4-[4-(difluoromethoxy)phenyl]-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate
and Hirshfeld surface analysis ofaDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Hacettepe University, 06100 Ankara, Türkiye, bDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Karadeniz Technical University, 61000 Trabzon, Türkiye, cDepartment of Physics, Faculty of Science, Eskisehir Technical University, Yunus Emre Campus 26470 Eskisehir, Türkiye, dDepartment of Physics, Faculty of Science, Erciyes University, 38039 Kayseri, Türkiye, eDepartment of Chemistry, Howard University, Washington DC 20059, USA, and fDepartment of Chemistry, M.M.A.M.C (Tribhuvan University), Biratnagar, Nepal
*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np
The 1,4-dihydropyridine ring of the title compound, C24H29F2NO4, adopts a distorted boat conformation, while the cyclohexene ring is in an almost twist-boat conformation. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds as well as C—H⋯π interactions connect molecules, forming layers parallel to the (100) plane. These layers are linked by and C—H⋯F interactions, which consolidate the Hirshfeld surface analysis shows the major contributions to the crystal packing are from H⋯H (54.1%), F⋯H/H⋯F (16.9%), O⋯H/H⋯O (15.4%) and C⋯H/H⋯C (12.6%) contacts.
Keywords: crystal structure; hydrogen bonds; van der Waals forces; C—H⋯F interactions; Hirshfeld surface analysis.
CCDC reference: 2271384
1. Chemical context
Inflammation is the natural and basic response of an organism to signals from tissue damage or pathogenic infections. In this way, the integrity of the organism is preserved. Chronic diseases that cause death and economic losses in the world are constantly increasing. It has been found that chronic diseases occur through inflammation-mediated mechanisms. In recent years, it has been proven that cardiovascular diseases, cancer, diabetes mellitus, chronic kidney disease, non-alcoholic fatty liver disease, autoimmune and neurodegenerative diseases are caused by inflammation. In this context, managing inflammatory mediators and inflammatory processes can be a treatment method for many chronic diseases (Furman et al., 2019; Tu et al., 2022).
Chronic or local inflammation first occurs with the activation of immune system cells such as cytokines, et al., 2022). The 1,4-DHP ring, which is a partially saturated derivative of the pyridine ring, is involved in the structure of many bioactive compounds. Nifedipine, which has a 1,4-DHP structure, was introduced as an antihypertensive treatment about 50 years ago (Fig. 1). The therapeutic success of nifedipine has led to the preparation of analogue derivatives. In this ongoing process, various compounds such as amlodipine and benidipine, which have a 1,4-DHP structure, are used as antihypertensives. Studies have shown that the 1,4-DHP ring has various activities such as neuroprotective, antiplatelet, anti-ischemic, anti-Alzheimer's, antituberculer, antiulcer and anticancer (Khot et al., 2021; Abdelwahab et al., 2022).
chemokines, oxygen-independent radicals, which generate signals from damaged cells or pathogens that are dangerous to the tissue. The immune system cells released in the circulatory system increase the pro-inflammatory response and reach the infected tissue area, but if this response is insufficient or excessive, the balance of the immune system is disturbed. This imbalance causes an excessive amount of distress signals and local or systemic tissue damage. This defect in the causes the inflammation to change from acute to chronic, and the disease progresses and results in death. A better understanding of inflammation and its processes enables the discovery of new and effective therapeutic ways to target and regulate inflammation. Drug therapy is widely used for the treatment of inflammation. Therefore, there is a need for new molecules that are more active and have minimal side effects (TuThe hexahydroquinoline ring system is obtained by condensing 1,4-DHP with cyclohexane. This ring system also has a variety of pharmacological activities such as calcium channel antagonist, anticancer, antimicrobial, anti-Alzheimer's. In current studies, 1,4-DHP derivatives and condensed analogues were found to be effective inflammation mediators of chronic inflammation in addition to their various biological activities.
In this study, the title compound, tert-butyl 4-[4-(difluoromethoxy)phenyl]-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate was obtained by using modified Hantzsch one-pot synthesis (Ghosh et al., 2013). The reaction of 4-difluoromethoxybenzaldehyde with 5,5-dimethylcyclohexane-1,3-dione and tert-butyl acetoacetate gives the target compound in methanol in the presence of ammonium acetate as nitrogen source (Çetin et al., 2022). The structure of the compound was elucidated by IR, 1H-NMR, 13C-NMR and HRMS analysis. X-ray analysis was undertaken to determine the Biological activity tests will be conducted in independent studies to determine the inhibition potential of inflammation mediators.
2. Structural commentary
As seen in Fig. 2, the 1,4-dihydropyridine ring (N1/C1/C6–C9) of the title compound adopts a distorted boat conformation [puckering parameters (Cremer & Pople, 1975) are QT = 0.2940 (18) Å, θ = 72.1 (4)° and φ = 182.9 (4)°], while the cyclohexene ring (C1–C6) has an almost twist-boat conformation [puckering parameters are QT = 0.4617 (19) Å, θ = 124.5 (2)° and φ = 313.8 (3)°]. The 4-[4-(difluoromethoxy]phenyl ring (C18–C23) makes a dihedral angle of 89.88 (7)° with the mean plane of the quinoline ring system [N1/C1–C9; maximum deviation = 0.358 (2) Å for C4]. The geometrical parameters of the title compound are in agreement with those reported for similar compounds in the Database survey section.
3. Supramolecular features and Hirshfeld surface analysis
The molecules in the crystal are connected by N—H⋯O and C—H⋯O hydrogen bonds, as well as C—H⋯π interactions, resulting in the formation of layers parallel to the (100) plane (see Table 1; Figs. 3 and 4). These layers are linked by and C—H⋯F interactions, which consolidate the (Fig. 5).
The Hirshfeld surfaces and their corresponding two-dimensional fingerprint plots were calculated using the Crystal Explorer 17.5 (Spackman et al., 2021) software package. The dnorm surfaces are mapped over a fixed colour scale from −0.5814 (red) to +1.6362 (blue) a.u. Red spots on the surface correspond to N⋯H/H⋯N and O⋯H/H⋯O interactions (Tables 1 and 2; Fig. 6a,b).
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Fingerprint plots of the most important non-covalent interactions for the title compound are shown in Fig. 7. The major contributions to the crystal packing are from H⋯H (54.1%), F⋯H/H⋯F (16.9%), O⋯H/H⋯O (15.4%) and C⋯H/H⋯C (12.6) contacts. N⋯H/H⋯N (0.5%), F⋯N/N⋯F (0.3%) and F⋯F (0.2%) contacts, which contribute less than 1%, are not shown in Fig. 7.
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 WEZJUK (Yıldırım et al., 2023), ECUCUE (Yıldırım et al., 2022), LOQCAX (Steiger et al., 2014), NEQMON (Öztürk Yıldırım 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 these compounds, molecules are linked by N—H⋯O hydrogen bonds. Furthermore, C—H⋯O hydrogen bonds in WEZJUK, ECUCUE, NEQMON, IMEJOA and PUGCIE and C—H⋯π interactions in WEZJUK and ECUCUE were also observed.
5. Synthesis and crystallization
The target compound was synthesized by refluxing 5,5-dimethylcyclohexane-1,3-dione (1 mmol), 4-difluoromethoxybenzaldehyde (1 mmol), tert-butylacetoacetate (1 mmol) and ammonium acetate (5 mmol) for 8 h in absolute methanol (10 ml). The reaction mixture was monitored by TLC, and after completion of the reaction was cooled to room temperature. The obtained precipitate was filtered and recrystallized from methanol for further purification. The synthetic route is shown in Fig. 8.
Yellow solid, m.p. 487–488 K; yield: 65.32%. IR (ν, cm−1) 3211 (N—H, stretching), 3080 (C—H stretching, aromatic), 2968 (C—H stretching, aliphatic) 1697 (C=O stretching, ester), 1641 (C=O stretching, ketone). 1H NMR (DMSO-d6) δ: 0.84 (3H; s; 7-CH3), 1.00 (3H; s; 7-CH3), 1.31 [9H, s, C(CH3)3], 1.95–1.99 (2H; d; J = 16 Hz; quinoline H8), 2.13–2.16 (H; d; J = 16.1; quinoline H8), 2.25 (3H; s; 2-CH3), 2.26–2.30 (H; d; J = 16.95 quinoline H6), 2.37–2.41 (H; d; J =1 6.95 quinoline H6), 4.78 (1H; s; quinoline H4), 6.99–7.01 (2H, d, J = 8.5 Hz Ar—H3), 7.14 (1H; t; J = 74.4 Hz; OCHF2), 7.17–7.18 (2H, d, J = 10 Ar—H2), 8.99 (1H,s; NH). 13C NMR (DMSO-d6) δ: 18.7 (2-CH3), 27.0 (7-CH3), 28.3 [COOC(CH3)3], 29.4 (C-7), 32.0 (C-8), 36.2 (C-4), 50.6 (C-6), 79.2 [COOC(CH3)3], 105.4 (C-3), 110.0 (C-4a), 114.8 (C3'), 116.9, 118.4, 118.9 (OCHF2), 129.4 (C2'), 144.5 (C1'), 145.3 (C-2), 149.3 (C-8a), 150.0 (C4'), 166.7 [COOC(CH3)3], 194.6 (C-5). HRMS (ESI/Q-TOF) m/z: [M + H]+ Calculated for C24H29F2NO4 433.2065; found 434.2328 (M + H).
6. Refinement
Crystal data, data collection and structure . The N-bound H atom was located in a difference Fourier map and refined freely [N1—H1N = 0.91 (2) Å]. All C-bound H atoms were positioned geometrically [C—H = 0.95–1.00 Å] and refined using a riding model with Uiso(H) = 1.2 or 1.5 Ueq(C).
details are summarized in Table 3
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Supporting information
CCDC reference: 2271384
https://doi.org/10.1107/S2056989023005455/zn2030sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023005455/zn2030Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023005455/zn2030Isup3.cml
Data collection: APEX2 (Bruker, 2018); cell
SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).C24H29F2NO4 | F(000) = 920 |
Mr = 433.48 | Dx = 1.281 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.6062 (11) Å | Cell parameters from 4059 reflections |
b = 9.7588 (7) Å | θ = 2.3–30.3° |
c = 13.1509 (9) Å | µ = 0.10 mm−1 |
β = 95.905 (2)° | T = 100 K |
V = 2247.5 (3) Å3 | Prism, colorless |
Z = 4 | 0.26 × 0.20 × 0.14 mm |
Bruker D8 Quest with Photon 2 detector diffractometer | 3208 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.111 |
Absorption correction: multi-scan (SADABS; Bruker, 2018) | θmax = 26.4°, θmin = 2.4° |
Tmin = 0.657, Tmax = 0.746 | h = −22→22 |
31708 measured reflections | k = −12→12 |
4599 independent reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: mixed |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0445P)2 + 0.5785P] where P = (Fo2 + 2Fc2)/3 |
4599 reflections | (Δ/σ)max = 0.001 |
290 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.92250 (6) | 0.20646 (12) | 0.49817 (9) | 0.0351 (3) | |
F2 | 0.86051 (6) | 0.08089 (11) | 0.59614 (9) | 0.0311 (3) | |
O1 | 0.78594 (7) | 0.91033 (13) | 0.37607 (9) | 0.0202 (3) | |
O2 | 0.51155 (7) | 0.57880 (16) | 0.12973 (10) | 0.0338 (4) | |
O3 | 0.54282 (7) | 0.65743 (13) | 0.28906 (9) | 0.0189 (3) | |
O4 | 0.80976 (7) | 0.27398 (13) | 0.54548 (9) | 0.0242 (3) | |
N1 | 0.74130 (8) | 0.64973 (15) | 0.07479 (12) | 0.0155 (3) | |
H1N | 0.7556 (11) | 0.634 (2) | 0.0116 (16) | 0.027 (6)* | |
C1 | 0.78375 (9) | 0.73899 (17) | 0.13677 (13) | 0.0141 (4) | |
C2 | 0.85366 (9) | 0.79398 (18) | 0.09469 (13) | 0.0160 (4) | |
H2A | 0.838042 | 0.864711 | 0.042740 | 0.019* | |
H2B | 0.878600 | 0.718755 | 0.060078 | 0.019* | |
C3 | 0.91163 (10) | 0.85665 (18) | 0.17650 (13) | 0.0164 (4) | |
C4 | 0.86773 (10) | 0.94844 (18) | 0.24516 (14) | 0.0184 (4) | |
H4A | 0.903915 | 0.984065 | 0.301593 | 0.022* | |
H4B | 0.846852 | 1.027890 | 0.204631 | 0.022* | |
C5 | 0.80277 (10) | 0.87635 (17) | 0.29047 (13) | 0.0155 (4) | |
C6 | 0.76121 (9) | 0.77274 (17) | 0.22958 (13) | 0.0140 (4) | |
C7 | 0.69507 (9) | 0.69774 (18) | 0.27054 (13) | 0.0146 (4) | |
H7A | 0.666791 | 0.764154 | 0.310637 | 0.018* | |
C8 | 0.64044 (10) | 0.64486 (17) | 0.18117 (13) | 0.0148 (4) | |
C9 | 0.66713 (9) | 0.61265 (18) | 0.09115 (13) | 0.0153 (4) | |
C10 | 0.96912 (11) | 0.9421 (2) | 0.12400 (15) | 0.0245 (4) | |
H10A | 1.008339 | 0.977719 | 0.175509 | 0.037* | |
H10B | 0.942644 | 1.018719 | 0.087535 | 0.037* | |
H10C | 0.993191 | 0.884569 | 0.075323 | 0.037* | |
C11 | 0.95397 (11) | 0.7439 (2) | 0.24056 (15) | 0.0257 (5) | |
H11A | 0.990465 | 0.785721 | 0.292795 | 0.039* | |
H11B | 0.981403 | 0.685259 | 0.196126 | 0.039* | |
H11C | 0.917130 | 0.688629 | 0.273739 | 0.039* | |
C12 | 0.62714 (10) | 0.5386 (2) | 0.00161 (14) | 0.0209 (4) | |
H12A | 0.588198 | 0.477760 | 0.025035 | 0.031* | |
H12B | 0.664249 | 0.484180 | −0.031788 | 0.031* | |
H12C | 0.602762 | 0.605142 | −0.047102 | 0.031* | |
C13 | 0.55921 (10) | 0.62201 (18) | 0.19487 (14) | 0.0174 (4) | |
C14 | 0.46412 (10) | 0.64012 (19) | 0.31875 (15) | 0.0212 (4) | |
C15 | 0.47276 (12) | 0.6890 (2) | 0.42836 (16) | 0.0338 (5) | |
H15A | 0.487156 | 0.786090 | 0.430522 | 0.051* | |
H15B | 0.512507 | 0.635304 | 0.467906 | 0.051* | |
H15C | 0.424214 | 0.677487 | 0.457741 | 0.051* | |
C16 | 0.44228 (11) | 0.4893 (2) | 0.31253 (16) | 0.0272 (5) | |
H16A | 0.438276 | 0.459295 | 0.241063 | 0.041* | |
H16B | 0.393032 | 0.476330 | 0.339800 | 0.041* | |
H16C | 0.481471 | 0.435070 | 0.352732 | 0.041* | |
C17 | 0.40767 (11) | 0.7291 (2) | 0.25328 (19) | 0.0358 (6) | |
H17A | 0.424720 | 0.824723 | 0.257522 | 0.054* | |
H17B | 0.357177 | 0.721817 | 0.278004 | 0.054* | |
H17C | 0.404679 | 0.698213 | 0.182077 | 0.054* | |
C18 | 0.72353 (10) | 0.57950 (18) | 0.34146 (13) | 0.0151 (4) | |
C19 | 0.77883 (10) | 0.48904 (19) | 0.31318 (14) | 0.0207 (4) | |
H19A | 0.796943 | 0.499218 | 0.248000 | 0.025* | |
C20 | 0.80838 (11) | 0.38451 (19) | 0.37706 (14) | 0.0218 (4) | |
H20A | 0.846835 | 0.325229 | 0.356664 | 0.026* | |
C21 | 0.78073 (10) | 0.36846 (18) | 0.47084 (14) | 0.0185 (4) | |
C22 | 0.72373 (10) | 0.45291 (19) | 0.49978 (14) | 0.0192 (4) | |
H22A | 0.703948 | 0.439405 | 0.563564 | 0.023* | |
C23 | 0.69559 (10) | 0.55749 (19) | 0.43512 (13) | 0.0179 (4) | |
H23A | 0.656394 | 0.615290 | 0.455307 | 0.021* | |
C24 | 0.85104 (11) | 0.16566 (19) | 0.51508 (15) | 0.0223 (4) | |
H24A | 0.824329 | 0.118997 | 0.453797 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0253 (6) | 0.0380 (7) | 0.0430 (8) | −0.0014 (5) | 0.0079 (5) | 0.0154 (6) |
F2 | 0.0389 (7) | 0.0244 (6) | 0.0305 (7) | 0.0009 (5) | 0.0062 (5) | 0.0127 (5) |
O1 | 0.0250 (7) | 0.0224 (7) | 0.0140 (7) | −0.0035 (6) | 0.0055 (5) | −0.0038 (5) |
O2 | 0.0210 (7) | 0.0590 (10) | 0.0214 (8) | −0.0140 (7) | 0.0026 (6) | −0.0078 (7) |
O3 | 0.0145 (6) | 0.0228 (7) | 0.0204 (7) | −0.0024 (5) | 0.0062 (5) | −0.0030 (6) |
O4 | 0.0342 (8) | 0.0217 (7) | 0.0169 (7) | 0.0053 (6) | 0.0039 (6) | 0.0042 (6) |
N1 | 0.0168 (8) | 0.0190 (8) | 0.0113 (8) | −0.0013 (6) | 0.0045 (6) | −0.0025 (6) |
C1 | 0.0139 (9) | 0.0133 (9) | 0.0149 (9) | 0.0020 (7) | 0.0001 (7) | 0.0013 (7) |
C2 | 0.0175 (9) | 0.0158 (9) | 0.0156 (9) | 0.0005 (7) | 0.0051 (7) | 0.0010 (7) |
C3 | 0.0165 (9) | 0.0166 (9) | 0.0166 (9) | −0.0011 (7) | 0.0035 (7) | −0.0002 (8) |
C4 | 0.0200 (10) | 0.0175 (9) | 0.0179 (10) | −0.0043 (8) | 0.0036 (8) | −0.0018 (8) |
C5 | 0.0173 (9) | 0.0146 (9) | 0.0147 (9) | 0.0031 (7) | 0.0014 (7) | 0.0022 (7) |
C6 | 0.0129 (9) | 0.0156 (9) | 0.0136 (9) | 0.0011 (7) | 0.0017 (7) | 0.0017 (7) |
C7 | 0.0150 (9) | 0.0158 (9) | 0.0135 (9) | −0.0009 (7) | 0.0040 (7) | −0.0001 (7) |
C8 | 0.0164 (9) | 0.0138 (9) | 0.0141 (9) | −0.0002 (7) | 0.0008 (7) | 0.0015 (7) |
C9 | 0.0150 (9) | 0.0150 (9) | 0.0158 (9) | −0.0006 (7) | 0.0010 (7) | 0.0025 (7) |
C10 | 0.0211 (10) | 0.0255 (11) | 0.0287 (11) | −0.0057 (8) | 0.0107 (8) | −0.0022 (9) |
C11 | 0.0203 (10) | 0.0299 (11) | 0.0265 (11) | 0.0033 (9) | −0.0001 (8) | 0.0027 (9) |
C12 | 0.0220 (10) | 0.0240 (10) | 0.0167 (10) | −0.0049 (8) | 0.0018 (8) | −0.0031 (8) |
C13 | 0.0185 (10) | 0.0183 (10) | 0.0156 (9) | −0.0012 (7) | 0.0024 (8) | 0.0009 (8) |
C14 | 0.0141 (9) | 0.0236 (10) | 0.0280 (11) | −0.0036 (8) | 0.0119 (8) | −0.0044 (8) |
C15 | 0.0263 (11) | 0.0417 (13) | 0.0362 (13) | −0.0094 (10) | 0.0172 (10) | −0.0157 (11) |
C16 | 0.0265 (11) | 0.0233 (11) | 0.0347 (12) | −0.0060 (9) | 0.0169 (9) | −0.0047 (9) |
C17 | 0.0184 (10) | 0.0345 (12) | 0.0560 (16) | 0.0035 (9) | 0.0117 (10) | 0.0062 (11) |
C18 | 0.0152 (9) | 0.0173 (9) | 0.0128 (9) | −0.0051 (7) | 0.0016 (7) | −0.0010 (7) |
C19 | 0.0262 (10) | 0.0224 (10) | 0.0146 (10) | 0.0007 (8) | 0.0072 (8) | 0.0007 (8) |
C20 | 0.0259 (10) | 0.0212 (10) | 0.0191 (10) | 0.0033 (8) | 0.0062 (8) | −0.0008 (8) |
C21 | 0.0223 (10) | 0.0163 (10) | 0.0165 (9) | −0.0032 (8) | −0.0003 (8) | 0.0010 (8) |
C22 | 0.0204 (10) | 0.0252 (10) | 0.0126 (9) | −0.0049 (8) | 0.0051 (7) | 0.0015 (8) |
C23 | 0.0149 (9) | 0.0230 (10) | 0.0161 (9) | −0.0027 (7) | 0.0035 (7) | −0.0019 (8) |
C24 | 0.0257 (11) | 0.0186 (10) | 0.0228 (10) | −0.0026 (8) | 0.0032 (8) | 0.0046 (8) |
F1—C24 | 1.360 (2) | C10—H10B | 0.9800 |
F2—C24 | 1.346 (2) | C10—H10C | 0.9800 |
O1—C5 | 1.238 (2) | C11—H11A | 0.9800 |
O2—C13 | 1.212 (2) | C11—H11B | 0.9800 |
O3—C13 | 1.346 (2) | C11—H11C | 0.9800 |
O3—C14 | 1.487 (2) | C12—H12A | 0.9800 |
O4—C24 | 1.366 (2) | C12—H12B | 0.9800 |
O4—C21 | 1.404 (2) | C12—H12C | 0.9800 |
N1—C1 | 1.363 (2) | C14—C15 | 1.511 (3) |
N1—C9 | 1.393 (2) | C14—C17 | 1.519 (3) |
N1—H1N | 0.91 (2) | C14—C16 | 1.521 (3) |
C1—C6 | 1.362 (2) | C15—H15A | 0.9800 |
C1—C2 | 1.500 (2) | C15—H15B | 0.9800 |
C2—C3 | 1.532 (2) | C15—H15C | 0.9800 |
C2—H2A | 0.9900 | C16—H16A | 0.9800 |
C2—H2B | 0.9900 | C16—H16B | 0.9800 |
C3—C10 | 1.530 (2) | C16—H16C | 0.9800 |
C3—C11 | 1.532 (2) | C17—H17A | 0.9800 |
C3—C4 | 1.536 (2) | C17—H17B | 0.9800 |
C4—C5 | 1.516 (2) | C17—H17C | 0.9800 |
C4—H4A | 0.9900 | C18—C23 | 1.389 (2) |
C4—H4B | 0.9900 | C18—C19 | 1.393 (2) |
C5—C6 | 1.442 (2) | C19—C20 | 1.388 (3) |
C6—C7 | 1.520 (2) | C19—H19A | 0.9500 |
C7—C8 | 1.530 (2) | C20—C21 | 1.381 (3) |
C7—C18 | 1.535 (2) | C20—H20A | 0.9500 |
C7—H7A | 1.0000 | C21—C22 | 1.382 (3) |
C8—C9 | 1.355 (2) | C22—C23 | 1.387 (3) |
C8—C13 | 1.477 (2) | C22—H22A | 0.9500 |
C9—C12 | 1.495 (2) | C23—H23A | 0.9500 |
C10—H10A | 0.9800 | C24—H24A | 1.0000 |
C13—O3—C14 | 120.42 (13) | C9—C12—H12B | 109.5 |
C24—O4—C21 | 118.04 (14) | H12A—C12—H12B | 109.5 |
C1—N1—C9 | 122.61 (15) | C9—C12—H12C | 109.5 |
C1—N1—H1N | 117.9 (13) | H12A—C12—H12C | 109.5 |
C9—N1—H1N | 116.9 (12) | H12B—C12—H12C | 109.5 |
C6—C1—N1 | 119.88 (16) | O2—C13—O3 | 122.80 (16) |
C6—C1—C2 | 124.75 (16) | O2—C13—C8 | 125.12 (17) |
N1—C1—C2 | 115.38 (15) | O3—C13—C8 | 112.06 (15) |
C1—C2—C3 | 113.36 (14) | O3—C14—C15 | 102.09 (14) |
C1—C2—H2A | 108.9 | O3—C14—C17 | 111.05 (15) |
C3—C2—H2A | 108.9 | C15—C14—C17 | 110.84 (17) |
C1—C2—H2B | 108.9 | O3—C14—C16 | 109.44 (14) |
C3—C2—H2B | 108.9 | C15—C14—C16 | 110.92 (17) |
H2A—C2—H2B | 107.7 | C17—C14—C16 | 112.07 (16) |
C10—C3—C11 | 109.42 (15) | C14—C15—H15A | 109.5 |
C10—C3—C2 | 108.94 (14) | C14—C15—H15B | 109.5 |
C11—C3—C2 | 110.54 (15) | H15A—C15—H15B | 109.5 |
C10—C3—C4 | 110.11 (15) | C14—C15—H15C | 109.5 |
C11—C3—C4 | 109.96 (15) | H15A—C15—H15C | 109.5 |
C2—C3—C4 | 107.85 (14) | H15B—C15—H15C | 109.5 |
C5—C4—C3 | 113.96 (14) | C14—C16—H16A | 109.5 |
C5—C4—H4A | 108.8 | C14—C16—H16B | 109.5 |
C3—C4—H4A | 108.8 | H16A—C16—H16B | 109.5 |
C5—C4—H4B | 108.8 | C14—C16—H16C | 109.5 |
C3—C4—H4B | 108.8 | H16A—C16—H16C | 109.5 |
H4A—C4—H4B | 107.7 | H16B—C16—H16C | 109.5 |
O1—C5—C6 | 122.52 (16) | C14—C17—H17A | 109.5 |
O1—C5—C4 | 119.59 (15) | C14—C17—H17B | 109.5 |
C6—C5—C4 | 117.87 (15) | H17A—C17—H17B | 109.5 |
C1—C6—C5 | 119.29 (15) | C14—C17—H17C | 109.5 |
C1—C6—C7 | 120.37 (15) | H17A—C17—H17C | 109.5 |
C5—C6—C7 | 120.29 (15) | H17B—C17—H17C | 109.5 |
C6—C7—C8 | 109.52 (14) | C23—C18—C19 | 117.37 (16) |
C6—C7—C18 | 111.30 (13) | C23—C18—C7 | 122.12 (16) |
C8—C7—C18 | 110.69 (14) | C19—C18—C7 | 120.51 (16) |
C6—C7—H7A | 108.4 | C20—C19—C18 | 122.20 (17) |
C8—C7—H7A | 108.4 | C20—C19—H19A | 118.9 |
C18—C7—H7A | 108.4 | C18—C19—H19A | 118.9 |
C9—C8—C13 | 119.93 (16) | C21—C20—C19 | 118.65 (17) |
C9—C8—C7 | 120.16 (15) | C21—C20—H20A | 120.7 |
C13—C8—C7 | 119.83 (15) | C19—C20—H20A | 120.7 |
C8—C9—N1 | 119.31 (16) | C20—C21—C22 | 120.74 (17) |
C8—C9—C12 | 128.53 (16) | C20—C21—O4 | 124.23 (16) |
N1—C9—C12 | 112.15 (15) | C22—C21—O4 | 114.93 (16) |
C3—C10—H10A | 109.5 | C21—C22—C23 | 119.59 (17) |
C3—C10—H10B | 109.5 | C21—C22—H22A | 120.2 |
H10A—C10—H10B | 109.5 | C23—C22—H22A | 120.2 |
C3—C10—H10C | 109.5 | C22—C23—C18 | 121.37 (17) |
H10A—C10—H10C | 109.5 | C22—C23—H23A | 119.3 |
H10B—C10—H10C | 109.5 | C18—C23—H23A | 119.3 |
C3—C11—H11A | 109.5 | F2—C24—F1 | 105.56 (14) |
C3—C11—H11B | 109.5 | F2—C24—O4 | 105.67 (15) |
H11A—C11—H11B | 109.5 | F1—C24—O4 | 110.52 (15) |
C3—C11—H11C | 109.5 | F2—C24—H24A | 111.6 |
H11A—C11—H11C | 109.5 | F1—C24—H24A | 111.6 |
H11B—C11—H11C | 109.5 | O4—C24—H24A | 111.6 |
C9—C12—H12A | 109.5 | ||
C9—N1—C1—C6 | 14.1 (2) | C7—C8—C9—C12 | 168.75 (17) |
C9—N1—C1—C2 | −165.54 (15) | C1—N1—C9—C8 | −12.6 (3) |
C6—C1—C2—C3 | 18.1 (2) | C1—N1—C9—C12 | 167.69 (16) |
N1—C1—C2—C3 | −162.30 (14) | C14—O3—C13—O2 | 2.1 (3) |
C1—C2—C3—C10 | −165.09 (15) | C14—O3—C13—C8 | −179.04 (14) |
C1—C2—C3—C11 | 74.64 (19) | C9—C8—C13—O2 | −2.2 (3) |
C1—C2—C3—C4 | −45.59 (19) | C7—C8—C13—O2 | −178.97 (18) |
C10—C3—C4—C5 | 172.96 (15) | C9—C8—C13—O3 | 179.00 (16) |
C11—C3—C4—C5 | −66.40 (19) | C7—C8—C13—O3 | 2.2 (2) |
C2—C3—C4—C5 | 54.20 (19) | C13—O3—C14—C15 | 178.94 (16) |
C3—C4—C5—O1 | 147.75 (16) | C13—O3—C14—C17 | −62.9 (2) |
C3—C4—C5—C6 | −34.2 (2) | C13—O3—C14—C16 | 61.4 (2) |
N1—C1—C6—C5 | −174.53 (15) | C6—C7—C18—C23 | 134.13 (17) |
C2—C1—C6—C5 | 5.1 (3) | C8—C7—C18—C23 | −103.82 (18) |
N1—C1—C6—C7 | 8.1 (2) | C6—C7—C18—C19 | −46.2 (2) |
C2—C1—C6—C7 | −172.29 (15) | C8—C7—C18—C19 | 75.88 (19) |
O1—C5—C6—C1 | −178.91 (16) | C23—C18—C19—C20 | −3.1 (3) |
C4—C5—C6—C1 | 3.1 (2) | C7—C18—C19—C20 | 177.17 (16) |
O1—C5—C6—C7 | −1.5 (3) | C18—C19—C20—C21 | 1.3 (3) |
C4—C5—C6—C7 | −179.50 (15) | C19—C20—C21—C22 | 1.3 (3) |
C1—C6—C7—C8 | −27.6 (2) | C19—C20—C21—O4 | −174.90 (16) |
C5—C6—C7—C8 | 155.05 (15) | C24—O4—C21—C20 | −20.1 (3) |
C1—C6—C7—C18 | 95.14 (19) | C24—O4—C21—C22 | 163.51 (16) |
C5—C6—C7—C18 | −82.24 (19) | C20—C21—C22—C23 | −1.9 (3) |
C6—C7—C8—C9 | 29.0 (2) | O4—C21—C22—C23 | 174.61 (15) |
C18—C7—C8—C9 | −94.12 (19) | C21—C22—C23—C18 | 0.0 (3) |
C6—C7—C8—C13 | −154.26 (15) | C19—C18—C23—C22 | 2.5 (3) |
C18—C7—C8—C13 | 82.65 (19) | C7—C18—C23—C22 | −177.84 (15) |
C13—C8—C9—N1 | 172.33 (15) | C21—O4—C24—F2 | −169.91 (14) |
C7—C8—C9—N1 | −10.9 (2) | C21—O4—C24—F1 | 76.36 (19) |
C13—C8—C9—C12 | −8.0 (3) |
Cg3 is the centroid of the C18–C23 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.91 (2) | 1.96 (2) | 2.866 (2) | 176.6 (18) |
C12—H12A···O2 | 0.98 | 2.25 | 2.800 (2) | 114 |
C16—H16A···O2 | 0.98 | 2.36 | 2.938 (2) | 117 |
C17—H17C···O2 | 0.98 | 2.37 | 2.958 (3) | 118 |
C20—H20A···F1 | 0.95 | 2.46 | 2.989 (2) | 115 |
C24—H24A···O1ii | 1.00 | 2.35 | 3.230 (2) | 147 |
C2—H2A···Cg3iii | 0.99 | 2.74 | 3.6959 (19) | 162 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, y−1, z; (iii) x, −y+1/2, z−3/2. |
H11C···H10A | 2.49 | 2 - x, -1/2 + y, 1/2 - z |
F2···H19A | 2.51 | x, 1/2 - y, 1/2 + z |
O1···H24A | 2.35 | x, 1 + y, z |
O1···H1N | 1.96 | x, 1/2 - y, -1/2 + z |
H12A···O2 | 2.61 | 1 - x, 1 - y, -z |
H15A···H12A | 2.40 | 1 - x, 1/2 + y, 1/2 - z |
H22A···H16B | 2.38 | 1 - x, 1 - y, 1 - z |
Acknowledgements
Authors' contributions are as follows. Conceptualization, RS and SÖY; methodology, RS and EP; investigation, RS and SÖY; writing (original draft), EP 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.
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