research communications
of anabolic steroid metabolite 4-chloroandrost-4-ene-3,17-dione
aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, (PERCH-CIC), Faculty of Science, Mahidol University, Rama 6 Road, Bangkok, 10400, Thailand, and bNational Center for Genetic Engineering and Biotechnology, National Science and Technology Development Agency, Thailand Science Park, Phathumthani 12120, Thailand
The title compound, NorClAD, C18H23ClO2, a metabolite of an anabolic steroid norchlorotestosterone acetate (NClTA), was successfully synthesized. Its molecular structure was characterized by 1H NMR and 13C NMR spectroscopy and single-crystal X-ray diffraction. The positions of the chlorine substituent, carbonyl groups and the double bond, as well as the of the molecule, were established. A Hirshfeld surface analysis was performed.
Keywords: anabolic steroid; doping agent; crystal structure; metabolite; testosterone; absolute configuration; Hirshfeld analysis.
CCDC reference: 2130048
1. Chemical context
Anabolic ). Norchlorotestosterone acetate (NClTA), one of the synthetic anabolic is applied by athletes as a testosterone mimetic for an improvement of their performance. The use of testosterone derivatives has therefore been banned by the World Anti-Doping Agency (WADA) (Wood & Stanton, 2012). The metabolism of anabolic is divided into two phases. In phase I, the of anabolic is converted into a more polar In phase II, the metabolite of anabolic is transformed to glucuronic acid or a sulfate derivative that may easily be eliminated from the human body. Knowledge of its metabolic pathway is therefore necessary to prove the illegal administration of NClTA.
have been reported to be used as growth-accelerating agents (Schanzer, 1996The metabolism of NClTA has been investigated successfully in invertebrates (Neomysis integer) and vertebrates (bovine) through oral and subcutaneous administration (Leyssens et al., 1994; Hendriks et al., 1994; Bizec et al., 1998). results indicate that one of the most abundant metabolites, found in both invertebrates and vertebrates (after subcutaneous injection), is 4-chloroandrost-4-ene-3,17-dione (NorClAD), the oxidized form of NClTA (see Fig. 1). NorClAD was synthesized through hydrolysis of NClTA followed by an oxidation (Hoof et al., 2004). However, elucidation of its crystal and molecular structures and its absolute stereochemistry were required. In this work, NorClAD was successfully synthesized in two steps according to the given scheme (Ringold et al., 1956), and its X-ray structure and absolute stereochemistry were determined.
2. Structural commentary
The molecular structure of the title compound is represented in Fig. 2. The compound consists of three six-membered rings A(C1–C4/C16/C17), B(C4/C5/C13–C16), C(C5–C8/C12/C13) and one five-membered ring D (C8–C12). Cyclohexenone ring A adopts a half-chair conformation while cyclohexane rings B and C adopt chair conformations. Cyclopentanone ring D adopts an with C12 as the flap. It is evident from the bond dimensions that the chlorine atom lies at C17, C1 and C9 are involved in carbonyl groups, and that the C16—C17 bond has double-bond character. The title compound adopts an all-trans ring junction and the absolute stereochemistry of atoms C4(R), C5(S) C8(S) C12(S) and C13(R) were properly determined using Cu Kα radiation and confirmed by the of 0.029 (4) (Parsons et al., 2013).
3. Supramolecular features and Hirshfeld surface analysis
A view of the unit-cell content of the title compound is presented in Fig. 3. There are several C—H⋯O and C—H⋯Cl contacts that can be considered as weak hydrogen bonds (see Table 1). In order to better understand the importance of these contacts, a Hirshfeld surface (Hirshfeld, 1977) was performed and the two-dimensional fingerprint plots were generated with Crystal Explorer 21.0 (Spackman et al., 2021). The Hirshfeld surface mapped over dnorm (see Fig. 4) is scaled between −0.1622 to 1.3540 a.u. The bright-red spots indicate the positions of the respective H-atom donors and H-atom acceptors (Venkatesan et al., 2016). Fig. 5 shows how these red spots correspond to short intermolecular contacts. The overall two-dimensional fingerprint plot and those delineated into H⋯H, H⋯Cl/Cl⋯H, H⋯O/O⋯H, H⋯C/C⋯H, Cl⋯C/C⋯Cl, and Cl⋯O/O⋯Cl contacts (McKinnon et al., 2007) are presented in Fig. 6a–g, respectively, together with their relative contributions to the Hirshfeld surface. The most abundant interaction is H⋯H, contributing 56.2% to the overall crystal packing, which is reflected in Fig. 6b as widely scattered points of high density owing to the large hydrogen content of the molecule. The blue region fingerprint plot of H⋯O/O⋯H interaction represents a symmetric distribution of points (22.8% contribution, Fig. 6d). While, the contribution of H⋯Cl/Cl⋯H contacts (Fig. 6c) is 13.7%. Percentages of other types of contacts are given in Table 2. The large number of H⋯H interactions indicate that van der Waals interactions play a major role in the crystal packing (Hathwar et al., 2015).
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4. Database survey
A search of Cambridge Structure Database (CSD, version 5.42, update of May 2021; Groom et al., 2016) found four structures that are closely related to the title compound and which play significant roles in the biological mechanisms. For the disordered structure of cortisol (11b,17a,21-trihydroxy-4-pregnene-3,20-dione), see CORTSL (Castellano, 1980). For dexamethasone at 119 K, see DEXMET11 (Raynor et al., 2007). For 17β-hydroxy-17a-methylandrostano[3,2-c]pyrazole, stanozolol, see AVENUL (Karpinska et al., 2011). For the Hirshfeld surface analysis, interaction energies, and DFT studies of cholesteryl heptanoate, see ZZZBIP01 (Akduran et al., 2021).
5. Synthesis and crystallization
The target compound was synthesized in two steps as shown in the scheme.
To a solution of norandrostenedione (5.00 g, 18.36 mmol) in methanol (100 mL) at 273 K were slowly added 30% H2O2 (4.5 mL, 57.55 mmol) and 6N NaOH (1.5 mL, 9.0 mmol). The mixture was then stirred at 273 K for 1 h. After that, the reaction solution was warmed up to room temperature and stirring continued for 2 h. After completion, water was added to the reaction mixture and the solvent was evaporated. The aqueous residue was extracted three times with ethyl acetate. The combined organic layer was dried over anhydrous Na2SO4 and then concentrated to dryness in vacuo to provide epoxide 1, which was used in the next step without further purification.
A solution of epoxide 1 (4.13 g) in acetone (100 mL) was treated with conc. HCl (1.5 mL) and the mixture was stirred at room temperature for 30 min. After that, water was added to the reaction mixture and it was extracted three times with dichloromethane. The combined organic extracts were dried over anhydrous Na2SO4 and evaporated to dryness. The solid product was recrystallized from MeOH:CH2Cl2 (3:1) at room temperature to provide 3.19 g of 4-chloroandrost-4-ene-3,17-dione (NorClAD) (56% yield).
Compound characterization: 1H NMR (400 MHz, chloroform-d) δ 3.42 (ddd, J = 15.0, 4.1, 2.4 Hz, 1H), 2.66 (dt, J = 16.2, 4.4 Hz, 1H), 2.55–2.36 (m, 2H), 2.36–2.25 (m, 2H), 2.19–2.08 (m, 2H), 2.07–1.92 (m, 3H), 1.88 (dt, J = 9.3, 2.7 Hz, 1H), 1.65–1.49 (m, 3H), 1.39–1.30 (m, 3H), 1.20 (tdd, J = 13.3, 11.7, 4.0 Hz, 1H), 1.05 0.97 (m, 1H), 0.95 (s, 3H). 13C NMR (101 MHz, chloroform-d) δ 220.3, 191.1, 159.6, 127.9, 50.1, 49.4, 47.7, 44.8, 39.7, 36.6, 35.8, 31.9, 31.3, 29.3, 25.7, 25.5, 21.7, 13.9.
6. Refinement
Crystal data, data collection and structure . All H atoms were positioned geometrically, with C—H = 0.98, 0.99 and 1.00 Å for methyl, methylene and methine protons, respectively, and refined as riding with Uiso(H) = 1.2 or 1.5Ueq(C). In addition, the of this compound was confirmed by the of 0.029 (4) (Parsons et al., 2013).
details are summarized in Table 3
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Supporting information
CCDC reference: 2130048
https://doi.org/10.1107/S2056989022010891/yk2175sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010891/yk2175Isup2.hkl
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C18H23ClO2 | Dx = 1.308 Mg m−3 |
Mr = 306.81 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 9974 reflections |
a = 7.4379 (4) Å | θ = 4.4–70.2° |
b = 12.7142 (6) Å | µ = 2.18 mm−1 |
c = 16.4790 (8) Å | T = 100 K |
V = 1558.37 (13) Å3 | Block, clear light colourless |
Z = 4 | 0.05 × 0.01 × 0.01 mm |
F(000) = 656 |
BRUKER D8 VENTURE diffractometer | 2907 independent reflections |
Radiation source: X-ray tube, Micro focus tube | 2787 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 70.1°, θmin = 4.4° |
ω and φ scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −15→15 |
Tmin = 0.678, Tmax = 0.753 | l = −20→19 |
18469 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.024 | w = 1/[σ2(Fo2) + (0.0383P)2 + 0.2052P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.065 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.17 e Å−3 |
2907 reflections | Δρmin = −0.18 e Å−3 |
191 parameters | Absolute structure: Flack x determined using 1150 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
0 restraints | Absolute structure parameter: 0.029 (4) |
Primary atom site location: dual |
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 | ||
Cl1 | 0.53413 (6) | −0.00451 (3) | 0.67248 (3) | 0.02851 (13) | |
O1 | 0.1878 (2) | −0.02569 (11) | 0.74872 (9) | 0.0345 (3) | |
O2 | 0.3004 (2) | 0.70098 (13) | 0.43229 (10) | 0.0401 (4) | |
C1 | 0.2157 (3) | 0.06557 (15) | 0.73085 (11) | 0.0242 (4) | |
C5 | 0.2976 (2) | 0.36358 (14) | 0.60909 (11) | 0.0191 (3) | |
H5 | 0.259997 | 0.323792 | 0.559582 | 0.023* | |
C6 | 0.1640 (2) | 0.45474 (14) | 0.62010 (12) | 0.0228 (4) | |
H6A | 0.188454 | 0.489661 | 0.672646 | 0.027* | |
H6B | 0.040622 | 0.425670 | 0.622443 | 0.027* | |
C17 | 0.3824 (2) | 0.09845 (14) | 0.68886 (11) | 0.0214 (4) | |
C3 | 0.0974 (2) | 0.24336 (14) | 0.69275 (11) | 0.0234 (4) | |
H3A | 0.017607 | 0.300838 | 0.711313 | 0.028* | |
H3B | 0.051866 | 0.217948 | 0.639818 | 0.028* | |
C7 | 0.1726 (2) | 0.53763 (15) | 0.55206 (12) | 0.0243 (4) | |
H7A | 0.128879 | 0.506525 | 0.500636 | 0.029* | |
H7B | 0.093792 | 0.597774 | 0.565909 | 0.029* | |
C4 | 0.2882 (2) | 0.28617 (13) | 0.68182 (11) | 0.0193 (3) | |
H4 | 0.319484 | 0.326567 | 0.731938 | 0.023* | |
C16 | 0.4260 (2) | 0.19893 (13) | 0.67251 (11) | 0.0206 (3) | |
C13 | 0.4912 (2) | 0.40302 (14) | 0.59430 (11) | 0.0197 (4) | |
H13 | 0.534533 | 0.439779 | 0.644250 | 0.024* | |
C9 | 0.4042 (3) | 0.64247 (15) | 0.46663 (12) | 0.0278 (4) | |
C15 | 0.6121 (3) | 0.23322 (15) | 0.64898 (13) | 0.0277 (4) | |
H15A | 0.684117 | 0.170390 | 0.634705 | 0.033* | |
H15B | 0.670068 | 0.267385 | 0.696210 | 0.033* | |
C2 | 0.0914 (3) | 0.15384 (15) | 0.75394 (12) | 0.0263 (4) | |
H2A | 0.125680 | 0.180934 | 0.808097 | 0.032* | |
H2B | −0.033061 | 0.126618 | 0.757601 | 0.032* | |
C8 | 0.3650 (2) | 0.57594 (14) | 0.54125 (11) | 0.0215 (4) | |
C18 | 0.4268 (3) | 0.64214 (15) | 0.61467 (12) | 0.0255 (4) | |
H18A | 0.340763 | 0.699209 | 0.624110 | 0.038* | |
H18B | 0.545813 | 0.671945 | 0.603545 | 0.038* | |
H18C | 0.433172 | 0.597296 | 0.662951 | 0.038* | |
C14 | 0.6134 (2) | 0.30946 (15) | 0.57747 (12) | 0.0262 (4) | |
H14A | 0.737587 | 0.334569 | 0.567856 | 0.031* | |
H14B | 0.572060 | 0.272622 | 0.527940 | 0.031* | |
C12 | 0.4880 (2) | 0.48125 (14) | 0.52440 (11) | 0.0221 (4) | |
H12 | 0.435207 | 0.443399 | 0.476847 | 0.027* | |
C10 | 0.5982 (3) | 0.62344 (17) | 0.44187 (13) | 0.0336 (5) | |
H10A | 0.671889 | 0.687004 | 0.451795 | 0.040* | |
H10B | 0.605681 | 0.605168 | 0.383565 | 0.040* | |
C11 | 0.6645 (3) | 0.53098 (16) | 0.49478 (13) | 0.0302 (4) | |
H11A | 0.735925 | 0.480383 | 0.462438 | 0.036* | |
H11B | 0.738045 | 0.556310 | 0.540879 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0383 (2) | 0.0235 (2) | 0.0237 (2) | 0.00946 (18) | 0.00264 (17) | 0.00324 (19) |
O1 | 0.0444 (8) | 0.0246 (7) | 0.0345 (8) | −0.0055 (6) | 0.0073 (7) | 0.0060 (6) |
O2 | 0.0503 (9) | 0.0395 (8) | 0.0305 (8) | 0.0078 (8) | 0.0007 (7) | 0.0141 (7) |
C1 | 0.0307 (9) | 0.0246 (9) | 0.0173 (9) | −0.0043 (8) | −0.0020 (7) | −0.0001 (7) |
C5 | 0.0164 (8) | 0.0212 (8) | 0.0198 (8) | −0.0009 (7) | 0.0004 (7) | −0.0029 (7) |
C6 | 0.0190 (8) | 0.0252 (9) | 0.0241 (10) | 0.0023 (7) | 0.0021 (7) | 0.0019 (7) |
C17 | 0.0263 (9) | 0.0229 (8) | 0.0151 (8) | 0.0034 (7) | −0.0013 (7) | −0.0013 (7) |
C3 | 0.0189 (8) | 0.0237 (9) | 0.0275 (10) | −0.0015 (7) | 0.0027 (7) | −0.0004 (7) |
C7 | 0.0212 (8) | 0.0279 (9) | 0.0237 (9) | 0.0042 (7) | −0.0011 (7) | 0.0033 (7) |
C4 | 0.0176 (7) | 0.0199 (8) | 0.0203 (8) | −0.0011 (6) | 0.0008 (7) | −0.0025 (7) |
C16 | 0.0206 (8) | 0.0229 (8) | 0.0183 (8) | 0.0011 (6) | −0.0004 (7) | −0.0018 (7) |
C13 | 0.0171 (8) | 0.0208 (8) | 0.0212 (9) | −0.0008 (7) | 0.0026 (6) | −0.0022 (7) |
C9 | 0.0387 (10) | 0.0246 (9) | 0.0202 (9) | −0.0019 (8) | 0.0012 (8) | −0.0007 (8) |
C15 | 0.0186 (8) | 0.0259 (9) | 0.0386 (11) | 0.0029 (7) | 0.0001 (8) | 0.0025 (8) |
C2 | 0.0260 (9) | 0.0277 (9) | 0.0253 (9) | −0.0046 (7) | 0.0060 (7) | 0.0006 (8) |
C8 | 0.0241 (9) | 0.0224 (8) | 0.0179 (8) | 0.0016 (7) | 0.0004 (7) | 0.0008 (7) |
C18 | 0.0320 (10) | 0.0232 (9) | 0.0211 (9) | 0.0018 (7) | −0.0011 (7) | 0.0001 (7) |
C14 | 0.0192 (8) | 0.0261 (9) | 0.0332 (10) | 0.0025 (7) | 0.0069 (8) | −0.0001 (8) |
C12 | 0.0214 (8) | 0.0242 (9) | 0.0207 (9) | −0.0007 (7) | 0.0031 (6) | −0.0026 (7) |
C10 | 0.0411 (11) | 0.0313 (11) | 0.0285 (10) | −0.0027 (9) | 0.0117 (9) | 0.0048 (8) |
C11 | 0.0281 (9) | 0.0302 (10) | 0.0323 (11) | −0.0007 (8) | 0.0109 (8) | 0.0021 (8) |
Cl1—C17 | 1.7493 (17) | C13—C14 | 1.523 (2) |
O1—C1 | 1.215 (2) | C13—C12 | 1.522 (3) |
O2—C9 | 1.212 (3) | C9—C8 | 1.521 (3) |
C1—C17 | 1.480 (3) | C9—C10 | 1.519 (3) |
C1—C2 | 1.503 (3) | C15—H15A | 0.9900 |
C5—H5 | 1.0000 | C15—H15B | 0.9900 |
C5—C6 | 1.538 (2) | C15—C14 | 1.526 (3) |
C5—C4 | 1.552 (2) | C2—H2A | 0.9900 |
C5—C13 | 1.544 (2) | C2—H2B | 0.9900 |
C6—H6A | 0.9900 | C8—C18 | 1.544 (3) |
C6—H6B | 0.9900 | C8—C12 | 1.538 (2) |
C6—C7 | 1.540 (3) | C18—H18A | 0.9800 |
C17—C16 | 1.345 (2) | C18—H18B | 0.9800 |
C3—H3A | 0.9900 | C18—H18C | 0.9800 |
C3—H3B | 0.9900 | C14—H14A | 0.9900 |
C3—C4 | 1.530 (2) | C14—H14B | 0.9900 |
C3—C2 | 1.521 (3) | C12—H12 | 1.0000 |
C7—H7A | 0.9900 | C12—C11 | 1.537 (2) |
C7—H7B | 0.9900 | C10—H10A | 0.9900 |
C7—C8 | 1.522 (3) | C10—H10B | 0.9900 |
C4—H4 | 1.0000 | C10—C11 | 1.544 (3) |
C4—C16 | 1.518 (2) | C11—H11A | 0.9900 |
C16—C15 | 1.502 (3) | C11—H11B | 0.9900 |
C13—H13 | 1.0000 | ||
O1—C1—C17 | 121.74 (18) | C16—C15—H15A | 109.0 |
O1—C1—C2 | 123.14 (18) | C16—C15—H15B | 109.0 |
C17—C1—C2 | 115.01 (15) | C16—C15—C14 | 112.91 (15) |
C6—C5—H5 | 107.2 | H15A—C15—H15B | 107.8 |
C6—C5—C4 | 110.95 (14) | C14—C15—H15A | 109.0 |
C6—C5—C13 | 112.12 (14) | C14—C15—H15B | 109.0 |
C4—C5—H5 | 107.2 | C1—C2—C3 | 111.88 (15) |
C13—C5—H5 | 107.2 | C1—C2—H2A | 109.2 |
C13—C5—C4 | 111.73 (14) | C1—C2—H2B | 109.2 |
C5—C6—H6A | 108.8 | C3—C2—H2A | 109.2 |
C5—C6—H6B | 108.8 | C3—C2—H2B | 109.2 |
C5—C6—C7 | 113.78 (15) | H2A—C2—H2B | 107.9 |
H6A—C6—H6B | 107.7 | C7—C8—C18 | 111.28 (15) |
C7—C6—H6A | 108.8 | C7—C8—C12 | 109.28 (15) |
C7—C6—H6B | 108.8 | C9—C8—C7 | 116.95 (16) |
C1—C17—Cl1 | 113.65 (13) | C9—C8—C18 | 105.85 (15) |
C16—C17—Cl1 | 121.62 (14) | C9—C8—C12 | 100.08 (14) |
C16—C17—C1 | 124.31 (16) | C12—C8—C18 | 113.01 (15) |
H3A—C3—H3B | 107.9 | C8—C18—H18A | 109.5 |
C4—C3—H3A | 109.3 | C8—C18—H18B | 109.5 |
C4—C3—H3B | 109.3 | C8—C18—H18C | 109.5 |
C2—C3—H3A | 109.3 | H18A—C18—H18B | 109.5 |
C2—C3—H3B | 109.3 | H18A—C18—H18C | 109.5 |
C2—C3—C4 | 111.81 (15) | H18B—C18—H18C | 109.5 |
C6—C7—H7A | 109.6 | C13—C14—C15 | 110.60 (15) |
C6—C7—H7B | 109.6 | C13—C14—H14A | 109.5 |
H7A—C7—H7B | 108.2 | C13—C14—H14B | 109.5 |
C8—C7—C6 | 110.07 (15) | C15—C14—H14A | 109.5 |
C8—C7—H7A | 109.6 | C15—C14—H14B | 109.5 |
C8—C7—H7B | 109.6 | H14A—C14—H14B | 108.1 |
C5—C4—H4 | 107.5 | C13—C12—C8 | 112.60 (14) |
C3—C4—C5 | 111.00 (14) | C13—C12—H12 | 106.5 |
C3—C4—H4 | 107.5 | C13—C12—C11 | 119.74 (15) |
C16—C4—C5 | 110.76 (14) | C8—C12—H12 | 106.5 |
C16—C4—C3 | 112.21 (14) | C11—C12—C8 | 104.11 (14) |
C16—C4—H4 | 107.5 | C11—C12—H12 | 106.5 |
C17—C16—C4 | 120.72 (15) | C9—C10—H10A | 110.6 |
C17—C16—C15 | 123.32 (16) | C9—C10—H10B | 110.6 |
C15—C16—C4 | 115.87 (14) | C9—C10—C11 | 105.83 (16) |
C5—C13—H13 | 108.8 | H10A—C10—H10B | 108.7 |
C14—C13—C5 | 109.38 (14) | C11—C10—H10A | 110.6 |
C14—C13—H13 | 108.8 | C11—C10—H10B | 110.6 |
C12—C13—C5 | 108.50 (14) | C12—C11—C10 | 102.70 (16) |
C12—C13—H13 | 108.8 | C12—C11—H11A | 111.2 |
C12—C13—C14 | 112.45 (15) | C12—C11—H11B | 111.2 |
O2—C9—C8 | 126.60 (18) | C10—C11—H11A | 111.2 |
O2—C9—C10 | 125.27 (19) | C10—C11—H11B | 111.2 |
C10—C9—C8 | 108.13 (16) | H11A—C11—H11B | 109.1 |
Cl1—C17—C16—C4 | 175.86 (13) | C7—C8—C12—C11 | 166.87 (15) |
Cl1—C17—C16—C15 | −7.7 (3) | C4—C5—C6—C7 | 177.20 (14) |
O1—C1—C17—Cl1 | −2.6 (2) | C4—C5—C13—C14 | 59.07 (19) |
O1—C1—C17—C16 | −175.31 (19) | C4—C5—C13—C12 | −177.92 (14) |
O1—C1—C2—C3 | −150.53 (19) | C4—C3—C2—C1 | −56.7 (2) |
O2—C9—C8—C7 | 30.3 (3) | C4—C16—C15—C14 | −48.3 (2) |
O2—C9—C8—C18 | −94.3 (2) | C16—C15—C14—C13 | 53.9 (2) |
O2—C9—C8—C12 | 148.1 (2) | C13—C5—C6—C7 | 51.5 (2) |
O2—C9—C10—C11 | −171.2 (2) | C13—C5—C4—C3 | −176.96 (14) |
C1—C17—C16—C4 | −12.0 (3) | C13—C5—C4—C16 | −51.60 (19) |
C1—C17—C16—C15 | 164.43 (18) | C13—C12—C11—C10 | −165.63 (16) |
C5—C6—C7—C8 | −52.9 (2) | C9—C8—C12—C13 | 174.71 (15) |
C5—C4—C16—C17 | −136.86 (17) | C9—C8—C12—C11 | 43.51 (18) |
C5—C4—C16—C15 | 46.5 (2) | C9—C10—C11—C12 | 18.2 (2) |
C5—C13—C14—C15 | −59.3 (2) | C2—C1—C17—Cl1 | 173.68 (13) |
C5—C13—C12—C8 | 58.98 (19) | C2—C1—C17—C16 | 1.0 (3) |
C5—C13—C12—C11 | −178.21 (16) | C2—C3—C4—C5 | 170.25 (14) |
C6—C5—C4—C3 | 57.13 (18) | C2—C3—C4—C16 | 45.7 (2) |
C6—C5—C4—C16 | −177.52 (14) | C8—C9—C10—C11 | 8.9 (2) |
C6—C5—C13—C14 | −175.66 (15) | C8—C12—C11—C10 | −38.77 (19) |
C6—C5—C13—C12 | −52.7 (2) | C18—C8—C12—C13 | 62.56 (19) |
C6—C7—C8—C9 | 168.92 (15) | C18—C8—C12—C11 | −68.63 (19) |
C6—C7—C8—C18 | −69.28 (19) | C14—C13—C12—C8 | −179.90 (15) |
C6—C7—C8—C12 | 56.2 (2) | C14—C13—C12—C11 | −57.1 (2) |
C17—C1—C2—C3 | 33.2 (2) | C12—C13—C14—C15 | −179.92 (15) |
C17—C16—C15—C14 | 135.14 (19) | C10—C9—C8—C7 | −149.86 (17) |
C3—C4—C16—C17 | −12.2 (2) | C10—C9—C8—C18 | 85.56 (18) |
C3—C4—C16—C15 | 171.12 (16) | C10—C9—C8—C12 | −32.04 (19) |
C7—C8—C12—C13 | −61.93 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O2i | 0.99 | 2.60 | 3.563 (2) | 165 |
C10—H10A···O2ii | 0.99 | 2.57 | 3.398 (3) | 141 |
C18—H18B···O2ii | 0.98 | 2.56 | 3.507 (3) | 163 |
C10—H10B···O1iii | 0.99 | 2.48 | 3.443 (3) | 164 |
C4—H4···Cl1iv | 1.00 | 2.88 | 3.8202 (18) | 158 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) x+1/2, −y+1/2, −z+1; (iv) −x+1, y+1/2, −z+3/2. |
Atom-atom interaction | Percentage |
H···H | 56.2 |
H···O/O···H | 22.8 |
H···Cl/Cl···H | 13.7 |
H···C/C···H | 5.6 |
Cl···O/O···Cl | 1.6 |
Cl···C/C···Cl | 0.2 |
Funding information
Financial support from Mahidol University, the Thailand Research Fund through the Royal Golden Jubilee PhD Program (grant No. PHD/0115/2557 for PS and TT) and the Center of Excellence for Innovation in Chemistry (PERCH-CIC) are gratefully acknowledged.
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