Crystal structure of (Z)-3-[5-chloro-2-(prop-2-yn­yloxy)phen­yl]-3-hy­droxy-1-[4-(tri­fluoro­meth­yl)phen­yl]­prop-2-en-1-one

The title compound, C₁₉H₁₂ClF₃O₃, obtained by the photochemical transformation of 2-[5-chloro-2-(prop-2-yn­yloxy)benzo­yl]-3-[4-(tri­fluoro­meth­yl)phen­yl]oxirane adopts a Z conformation with respect to the enolic C=C double bond. The dihedral angle between the benzene rings is 12.25 (16)° and an intra­molecular O—H...O hydrogen bond closes an S(6) ring. An intra­molecular C—H...O inter­action also leads to an S(6) ring. In the crystal, very weak C—H...O inter­actions and short Cl...Cl contacts [3.3221 (16) Å] are seen, as well as weak aromatic π–π stacking inter­actions [centroid–centroid separation = 3.879 (2) Å].

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.068
• wR factor = 0.191
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0045 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B    ..  O1      ..       2.62 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      7.097 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         12 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT093_ALERT_1_G No su's on H-positions, refinement reported as .      mixed Check
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00200 Degree
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        273 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        273 Check
PLAT242_ALERT_2_G Low       Ueq as Compared to Neighbors for .....        C19 Check
PLAT434_ALERT_2_G Short Inter HL..HL Contact Cl1    ..  Cl1     ..       3.32 Ang.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         36 Do !
            O3  -C7  -C8  -C9   -158.00 26.00   1.555   1.555   1.555   1.555
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          59 %

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Chemical context

The functionalized β-hy­droxy­enones (or 1,3-diketones) are medicinal significant compounds showing anti­viral (Diana et al., 1978), insecticidal (Crouse et al., 1989), anti-sunscreen (Andrae et al., 1997), anti­oxidant (Nishiyama et al., 2002), and more important HIV-1 Integrase (IN) inhibitor (Tchertanov & Mouscadet, 2007) activity. Also, 1,3-diketones are the building blocks for the synthesis of core heterocycles (Sheikh et al., 2009), and biologically important metal complexes (Sheikh et al., 2013). Our inter­est in the catalyst free photochemical organic transformation led us to synthesize the title compound and we report herein on its crystal structure (Fig. 1).

S2. Synthesis and crystallization

A de­oxy­genated solution of 2-{5-chloro-2-(prop-2-ynyl­oxy)benzoyl}-3-{4-(tri­fluoro­methyl)­phenyl}­oxirane (2.0 mmol, 760 mg) in aceto­nitrile (100 ml) contained in a Pyrex glass vessel was purged with N₂ for 30 min. and then irradiated under N₂ atmosphere with light from a 125W Hg-vapor lamp for 90 min. The removal of solvent under reduced pressure yielded a gummy mass that was chromatographed over a silica gel column. The column was eluted with increasing proportion of ethyl acetate in pet ether-ethyl acetate mixture to obtain the desired photoproduct. In addition to this, another photoproduct 8-chloro-2-(4-tri­fluoro­methyl­phenyl) benzo[b]furo[2,3-e]oxepin-10(4H)-one was also separated from the photolysate. The resulting pale yellow solid was filtered, washed several times with pet ether and then dried in vacuo overnight to yield the desired (Z)-3-{5-chloro-2-(prop-2-ynyl­oxy)phenyl}-1-{4-(tri­fluoro­methyl)­phenyl}-3-hy­droxy­prop-2-en-1-one, (267 mg, 35% yield). The pale yellow re­cta­ngular crystals, suitable for X-ray structure analysis, were obtained by recrystallization from ethanol by slow evaporation at room temperature after several days (m.p. 383-385 K).

FT—IR (KBr) ν: 3418 (-OH), 2150 (C≡C), 1713 (C=O), 1605 (C=C) cm^-1; ¹H NMR (400 MHz, CDCl₃) δ, ppm: 8.08 (2H, d, J = 8.2 Hz, H-3'', 5''), 7.95 (1H, d, J = 2.7 Hz, H-6'), 7.73 (2H, d, J = 8.3 Hz, H-2'', 6''), 7.44 (1H, dd, J = 8.8, 2.7 Hz, H-4'), 7.23(1H, s, H-2), 7.03 (1H, d, J = 8.8 Hz, H-3'), 4.82 (2H, d, J = 2.4 Hz, OCH₂-1'''), 2.63 (1H, t, J = 2.3 Hz, ≡CH-3'''); ¹³C NMR (100 MHz, CDCl₃):δ, ppm: 57.00, 99.21, 114.67, 122.34, 125.05, 125.63,126.58, 127.40, 127.62, 130.30, 132.84, 133.54, 133.86, 138.72, 154.99, 183.24, 183.69.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined anisotropically. The positions of the hydrogen atoms were fixed according to a riding model and were refined isotropically.

Related literature

For background to 1,3-diketones, see: Andrae et al. (1997); Crouse et al. (1989); Diana et al. (1978); Nishiyama et al. (2002); Sheikh et al. (2009, 2013); Tchertanov & Mouscadet (2007).

Structure description

The functionalized β-hy­droxy­enones (or 1,3-diketones) are medicinal significant compounds showing anti­viral (Diana et al., 1978), insecticidal (Crouse et al., 1989), anti-sunscreen (Andrae et al., 1997), anti­oxidant (Nishiyama et al., 2002), and more important HIV-1 Integrase (IN) inhibitor (Tchertanov & Mouscadet, 2007) activity. Also, 1,3-diketones are the building blocks for the synthesis of core heterocycles (Sheikh et al., 2009), and biologically important metal complexes (Sheikh et al., 2013). Our inter­est in the catalyst free photochemical organic transformation led us to synthesize the title compound and we report herein on its crystal structure (Fig. 1).

For background to 1,3-diketones, see: Andrae et al. (1997); Crouse et al. (1989); Diana et al. (1978); Nishiyama et al. (2002); Sheikh et al. (2009, 2013); Tchertanov & Mouscadet (2007).

Synthesis and crystallization

A de­oxy­genated solution of 2-{5-chloro-2-(prop-2-ynyl­oxy)benzoyl}-3-{4-(tri­fluoro­methyl)­phenyl}­oxirane (2.0 mmol, 760 mg) in aceto­nitrile (100 ml) contained in a Pyrex glass vessel was purged with N₂ for 30 min. and then irradiated under N₂ atmosphere with light from a 125W Hg-vapor lamp for 90 min. The removal of solvent under reduced pressure yielded a gummy mass that was chromatographed over a silica gel column. The column was eluted with increasing proportion of ethyl acetate in pet ether-ethyl acetate mixture to obtain the desired photoproduct. In addition to this, another photoproduct 8-chloro-2-(4-tri­fluoro­methyl­phenyl) benzo[b]furo[2,3-e]oxepin-10(4H)-one was also separated from the photolysate. The resulting pale yellow solid was filtered, washed several times with pet ether and then dried in vacuo overnight to yield the desired (Z)-3-{5-chloro-2-(prop-2-ynyl­oxy)phenyl}-1-{4-(tri­fluoro­methyl)­phenyl}-3-hy­droxy­prop-2-en-1-one, (267 mg, 35% yield). The pale yellow re­cta­ngular crystals, suitable for X-ray structure analysis, were obtained by recrystallization from ethanol by slow evaporation at room temperature after several days (m.p. 383-385 K).

FT—IR (KBr) ν: 3418 (-OH), 2150 (C≡C), 1713 (C=O), 1605 (C=C) cm^-1; ¹H NMR (400 MHz, CDCl₃) δ, ppm: 8.08 (2H, d, J = 8.2 Hz, H-3'', 5''), 7.95 (1H, d, J = 2.7 Hz, H-6'), 7.73 (2H, d, J = 8.3 Hz, H-2'', 6''), 7.44 (1H, dd, J = 8.8, 2.7 Hz, H-4'), 7.23(1H, s, H-2), 7.03 (1H, d, J = 8.8 Hz, H-3'), 4.82 (2H, d, J = 2.4 Hz, OCH₂-1'''), 2.63 (1H, t, J = 2.3 Hz, ≡CH-3'''); ¹³C NMR (100 MHz, CDCl₃):δ, ppm: 57.00, 99.21, 114.67, 122.34, 125.05, 125.63,126.58, 127.40, 127.62, 130.30, 132.84, 133.54, 133.86, 138.72, 154.99, 183.24, 183.69.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined anisotropically. The positions of the hydrogen atoms were fixed according to a riding model and were refined isotropically.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Molecular structure of the title compound showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view along the a axis of the inter- and intramolecular hydrogen bonds in the title compound (shown as dashed lines, see Table 1 for details). Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.
	Fig. 3. A view along the a axis showing F···F and Cl···Cl contact distances (dashed lines). Hydrogen atoms not involved in the interactions are excluded for clarity.
	Fig. 4. A partial view along b axis of the π–π interactions (dashed lines) in the crystal packing of the title compound. All hydrogen atoms are omitted for clarity.

(Z)-3-[5-Chloro-2-(prop-2-ynyloxy)phenyl]-3-hydroxy-1-[4-(trifluoromethyl)phenyl]prop-2-en-1-one

Crystal data

C19H12ClF3O3	Z = 2
Mr = 380.74	F(000) = 388.0
Triclinic, P1	Dx = 1.476 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2203 (12) Å	Cell parameters from 3035 reflections
b = 9.3822 (14) Å	θ = 2.3–25.6°
c = 12.3140 (18) Å	µ = 0.27 mm^−1
α = 90.150 (2)°	T = 273 K
β = 109.201 (2)°	Block, colorless
γ = 106.212 (2)°	0.34 × 0.29 × 0.14 mm
V = 856.5 (2) Å^3

Data collection

Bruker SMART CCD diffractometer	3016 independent reflections
Radiation source: fine-focus sealed tube	2503 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
Tmin = 0.912, Tmax = 0.962	k = −11→11
8272 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0963P)^2 + 0.390P] where P = (Fo^2 + 2Fc^2)/3
3003 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.10694 (14)	1.10578 (13)	1.42182 (7)	0.0913 (4)
O3	0.2888 (3)	1.16996 (19)	0.99885 (16)	0.0600 (5)
O2	0.1279 (3)	0.7541 (2)	1.1146 (2)	0.0766 (7)
H24	0.1237	0.6813	1.0756	0.115*
C13	0.2457 (4)	0.7250 (3)	0.8037 (2)	0.0508 (6)
C12	0.2108 (4)	0.7295 (3)	0.9149 (2)	0.0525 (7)
C4	0.1949 (3)	1.0149 (3)	1.1317 (2)	0.0474 (6)
C2	0.1511 (4)	1.0020 (3)	1.2318 (2)	0.0558 (7)
H2	0.1147	0.9080	1.2557	0.067*
C6	0.2471 (3)	1.1588 (3)	1.0975 (2)	0.0485 (6)
C10	0.1852 (3)	0.8758 (3)	1.0691 (2)	0.0493 (6)
C11	0.2284 (4)	0.8668 (3)	0.9711 (2)	0.0531 (7)
H11	0.2707	0.9545	0.9408	0.064*
C15	0.3271 (4)	0.8532 (3)	0.7619 (3)	0.0585 (7)
H15	0.3643	0.9449	0.8054	0.070*
C18	0.3000 (4)	0.7117 (3)	0.5930 (2)	0.0575 (7)
C5	0.2558 (4)	1.2823 (3)	1.1638 (3)	0.0602 (7)
H5	0.2906	1.3771	1.1410	0.072*
C17	0.3537 (4)	0.8470 (3)	0.6579 (3)	0.0618 (7)
H17	0.4077	0.9339	0.6313	0.074*
C1	0.1610 (4)	1.1259 (4)	1.2959 (2)	0.0620 (8)
F3	0.4185 (4)	0.8295 (3)	0.4541 (2)	0.1194 (9)
C7	0.3400 (4)	1.3122 (3)	0.9602 (3)	0.0611 (7)
H7A	0.4485	1.3760	1.0179	0.073*
H7B	0.2448	1.3590	0.9473	0.073*
C14	0.1936 (4)	0.5899 (3)	0.7376 (3)	0.0633 (8)
H14	0.1400	0.5026	0.7641	0.076*
C3	0.2136 (4)	1.2658 (4)	1.2624 (3)	0.0656 (8)
H3	0.2204	1.3491	1.3067	0.079*
C8	0.3725 (5)	1.2911 (4)	0.8531 (3)	0.0750 (9)
C16	0.2202 (5)	0.5826 (3)	0.6329 (3)	0.0686 (8)
H16	0.1844	0.4911	0.5893	0.082*
C19	0.3237 (5)	0.7041 (4)	0.4781 (3)	0.0763 (9)
C9	0.3999 (8)	1.2763 (5)	0.7678 (4)	0.1171 (17)
H9	0.4219	1.2645	0.6994	0.140*
F2	0.1707 (4)	0.6729 (5)	0.3933 (2)	0.1649 (15)
F1	0.4002 (7)	0.6064 (4)	0.4652 (3)	0.1871 (19)
O1	0.1593 (3)	0.6070 (2)	0.9541 (2)	0.0759 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0980 (7)	0.1272 (9)	0.0637 (6)	0.0341 (6)	0.0464 (5)	0.0084 (5)
O3	0.0908 (14)	0.0395 (10)	0.0603 (12)	0.0176 (9)	0.0411 (11)	0.0111 (8)
O2	0.1181 (19)	0.0490 (12)	0.0843 (15)	0.0281 (12)	0.0595 (14)	0.0234 (10)
C13	0.0497 (14)	0.0436 (14)	0.0584 (16)	0.0184 (11)	0.0138 (12)	0.0050 (12)
C12	0.0546 (15)	0.0452 (14)	0.0606 (16)	0.0198 (12)	0.0194 (13)	0.0107 (12)
C4	0.0428 (13)	0.0516 (15)	0.0478 (14)	0.0153 (11)	0.0147 (11)	0.0084 (11)
C2	0.0511 (15)	0.0652 (17)	0.0518 (15)	0.0155 (13)	0.0199 (12)	0.0142 (13)
C6	0.0479 (14)	0.0473 (14)	0.0502 (14)	0.0137 (11)	0.0168 (11)	0.0048 (11)
C10	0.0491 (14)	0.0440 (14)	0.0553 (15)	0.0151 (11)	0.0173 (12)	0.0134 (11)
C11	0.0618 (16)	0.0408 (14)	0.0579 (16)	0.0137 (12)	0.0235 (13)	0.0104 (12)
C15	0.0625 (17)	0.0463 (15)	0.0667 (18)	0.0101 (13)	0.0272 (14)	−0.0019 (13)
C18	0.0556 (16)	0.0593 (17)	0.0560 (16)	0.0204 (13)	0.0145 (13)	0.0020 (13)
C5	0.0659 (18)	0.0521 (16)	0.0641 (17)	0.0166 (13)	0.0252 (15)	0.0005 (13)
C17	0.0632 (17)	0.0519 (16)	0.0696 (19)	0.0092 (13)	0.0284 (15)	0.0047 (14)
C1	0.0552 (16)	0.084 (2)	0.0492 (15)	0.0215 (15)	0.0204 (13)	0.0054 (14)
F3	0.152 (2)	0.1049 (18)	0.1022 (17)	−0.0047 (16)	0.0797 (17)	−0.0060 (14)
C7	0.0781 (19)	0.0425 (14)	0.0730 (19)	0.0208 (13)	0.0367 (16)	0.0161 (13)
C14	0.082 (2)	0.0418 (15)	0.0623 (18)	0.0163 (14)	0.0211 (15)	0.0068 (13)
C3	0.0672 (18)	0.071 (2)	0.0613 (18)	0.0240 (15)	0.0219 (15)	−0.0085 (15)
C8	0.109 (3)	0.0563 (18)	0.085 (2)	0.0361 (18)	0.057 (2)	0.0315 (16)
C16	0.091 (2)	0.0459 (16)	0.0621 (18)	0.0197 (15)	0.0182 (16)	−0.0030 (13)
C19	0.094 (3)	0.067 (2)	0.062 (2)	0.0193 (19)	0.0233 (19)	−0.0047 (16)
C9	0.196 (5)	0.104 (3)	0.111 (3)	0.073 (3)	0.105 (4)	0.051 (3)
F2	0.118 (2)	0.248 (4)	0.0599 (14)	−0.032 (2)	0.0136 (14)	0.0125 (18)
F1	0.372 (6)	0.176 (3)	0.126 (2)	0.180 (4)	0.148 (3)	0.048 (2)
O1	0.1138 (18)	0.0424 (11)	0.0871 (15)	0.0259 (11)	0.0525 (14)	0.0177 (10)

Geometric parameters (Å, º)

Cl1—C1	1.745 (3)	C18—C17	1.377 (4)
O3—C6	1.364 (3)	C18—C16	1.382 (4)
O3—C7	1.416 (3)	C18—C19	1.494 (4)
O2—C10	1.310 (3)	C5—C3	1.366 (4)
O2—H24	0.8200	C5—H5	0.9300
C13—C14	1.384 (4)	C17—H17	0.9300
C13—C15	1.393 (4)	C1—C3	1.372 (5)
C13—C12	1.491 (4)	F3—C19	1.312 (4)
C12—O1	1.265 (3)	C7—C8	1.452 (4)
C12—C11	1.409 (4)	C7—H7A	0.9700
C4—C2	1.390 (4)	C7—H7B	0.9700
C4—C6	1.408 (4)	C14—C16	1.381 (4)
C4—C10	1.484 (4)	C14—H14	0.9300
C2—C1	1.371 (4)	C3—H3	0.9300
C2—H2	0.9300	C8—C9	1.161 (5)
C6—C5	1.388 (4)	C16—H16	0.9300
C10—C11	1.373 (4)	C19—F1	1.283 (4)
C11—H11	0.9300	C19—F2	1.299 (4)
C15—C17	1.372 (4)	C9—H9	0.9300
C15—H15	0.9300
C6—O3—C7	119.4 (2)	C6—C5—H5	119.7
C10—O2—H24	109.5	C15—C17—C18	119.8 (3)
C14—C13—C15	117.9 (3)	C15—C17—H17	120.1
C14—C13—C12	119.7 (3)	C18—C17—H17	120.1
C15—C13—C12	122.4 (2)	C2—C1—C3	120.8 (3)
O1—C12—C11	121.7 (3)	C2—C1—Cl1	119.7 (3)
O1—C12—C13	118.0 (2)	C3—C1—Cl1	119.5 (2)
C11—C12—C13	120.2 (2)	O3—C7—C8	107.8 (2)
C2—C4—C6	117.9 (2)	O3—C7—H7A	110.1
C2—C4—C10	117.5 (2)	C8—C7—H7A	110.1
C6—C4—C10	124.6 (2)	O3—C7—H7B	110.1
C1—C2—C4	120.9 (3)	C8—C7—H7B	110.1
C1—C2—H2	119.6	H7A—C7—H7B	108.5
C4—C2—H2	119.6	C16—C14—C13	121.0 (3)
O3—C6—C5	122.6 (2)	C16—C14—H14	119.5
O3—C6—C4	117.4 (2)	C13—C14—H14	119.5
C5—C6—C4	120.0 (3)	C5—C3—C1	119.8 (3)
O2—C10—C11	120.1 (2)	C5—C3—H3	120.1
O2—C10—C4	114.1 (2)	C1—C3—H3	120.1
C11—C10—C4	125.9 (2)	C9—C8—C7	179.0 (4)
C10—C11—C12	122.4 (2)	C14—C16—C18	119.9 (3)
C10—C11—H11	118.8	C14—C16—H16	120.1
C12—C11—H11	118.8	C18—C16—H16	120.1
C17—C15—C13	121.4 (3)	F1—C19—F2	106.7 (4)
C17—C15—H15	119.3	F1—C19—F3	105.4 (4)
C13—C15—H15	119.3	F2—C19—F3	103.3 (3)
C17—C18—C16	120.0 (3)	F1—C19—C18	113.8 (3)
C17—C18—C19	120.2 (3)	F2—C19—C18	111.9 (3)
C16—C18—C19	119.8 (3)	F3—C19—C18	114.9 (3)
C3—C5—C6	120.6 (3)	C8—C9—H9	180.0
C3—C5—H5	119.7
C14—C13—C12—O1	10.5 (4)	C4—C6—C5—C3	−0.2 (4)
C15—C13—C12—O1	−170.5 (3)	C13—C15—C17—C18	−0.4 (5)
C14—C13—C12—C11	−167.0 (3)	C16—C18—C17—C15	−0.2 (4)
C15—C13—C12—C11	12.0 (4)	C19—C18—C17—C15	178.4 (3)
C6—C4—C2—C1	−0.9 (4)	C4—C2—C1—C3	0.3 (4)
C10—C4—C2—C1	178.5 (2)	C4—C2—C1—Cl1	−179.5 (2)
C7—O3—C6—C5	−1.2 (4)	C6—O3—C7—C8	−178.7 (3)
C7—O3—C6—C4	179.3 (2)	C15—C13—C14—C16	−0.6 (4)
C2—C4—C6—O3	−179.7 (2)	C12—C13—C14—C16	178.4 (3)
C10—C4—C6—O3	1.0 (4)	C6—C5—C3—C1	−0.4 (5)
C2—C4—C6—C5	0.8 (4)	C2—C1—C3—C5	0.4 (5)
C10—C4—C6—C5	−178.5 (3)	Cl1—C1—C3—C5	−179.9 (2)
C2—C4—C10—O2	2.7 (4)	O3—C7—C8—C9	−158 (26)
C6—C4—C10—O2	−178.0 (2)	C13—C14—C16—C18	0.1 (5)
C2—C4—C10—C11	−177.9 (3)	C17—C18—C16—C14	0.3 (5)
C6—C4—C10—C11	1.3 (4)	C19—C18—C16—C14	−178.2 (3)
O2—C10—C11—C12	1.0 (4)	C17—C18—C19—F1	130.3 (4)
C4—C10—C11—C12	−178.2 (2)	C16—C18—C19—F1	−51.1 (5)
O1—C12—C11—C10	−2.2 (4)	C17—C18—C19—F2	−108.6 (4)
C13—C12—C11—C10	175.2 (2)	C16—C18—C19—F2	69.9 (4)
C14—C13—C15—C17	0.7 (4)	C17—C18—C19—F3	8.7 (5)
C12—C13—C15—C17	−178.3 (3)	C16—C18—C19—F3	−172.7 (3)
O3—C6—C5—C3	−179.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H24···O1	0.82	1.79	2.529 (3)	149
C11—H11···O3	0.93	2.09	2.747 (3)	126
C7—H7B···O1^i	0.97	2.62	3.476 (4)	147

Symmetry code: (i) x, y+1, z.