(R,E)-3-(4-Chloro­phen­yl)-1-phenyl­allyl 4-nitro­benzoate

Troshin, K.; Mayer, P.; Mayr, H.

doi:10.1107/S1600536812032813

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2549

https://doi.org/10.1107/S1600536812032813

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(R,E)-3-(4-Chlorophenyl)-1-phenylallyl 4-nitrobenzoate

Konstantin Troshin,^a Peter Mayer ^a ^* and Herbert Mayr ^a

^aLudwig-Maximilians-Universität, Department, Butenandtstrasse 5–13, 81377 München, Germany
^*Correspondence e-mail: p.mayer@lmu.de

(Received 19 July 2012; accepted 19 July 2012; online 25 July 2012)

The title compound, C₂₂H₁₆ClNO₄, adopts a conformation in which the phenyl ring plane forms similar dihedral angles with the nitrobenzoate C₆ ring [76.97 (8)°] and the chlorophenyl group [76.95 (8)°]; the dihedral angle between the chlorophenyl and nitrobenzoate rings is 66.43 (8)°. In the crystal, π–π stacking is observed between the latter two planes, with a dihedral angle of 1.79 (8)° and a centroid–centroid distance of 3.735 (1) Å. In addition, molecules are linked along [100] by weak C—H⋯O contacts.

Related literature

For background to the stereochemistry of allylic rearrangements, see: Hughes (1941 ); Raber et al. (1974 ); Goering et al. (1971 ). For details of the synthesis, see: Troshin et al. (2011 ); Gao et al. (1987 ); Roos & Donovan (1996 ). For related structures, see: Cao et al. (2011 ); Wang et al. (2009 ).

Experimental

Crystal data

C₂₂H₁₆ClNO₄
M_r = 393.82
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.3817 (1) Å
b = 9.9238 (2) Å
c = 22.8090 (4) Å
V = 1897.21 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 173 K
0.28 × 0.15 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
12403 measured reflections
4331 independent reflections
3847 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.083
S = 1.03
4331 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983), 1854 Friedel pairs
Flack parameter: 0.01 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O4ⁱ	0.95	2.59	3.529 (2)	168
C12—H12⋯Cgⁱⁱ	0.95	2.92	3.8072 (19)	157
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y, z.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812032813/gg2092sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032813/gg2092Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812032813/gg2092Isup3.cml

checkCIF report

Comment top

Allylic substances have been used since 1940s to get an insight into the detailed mechanism of S_N1 reactions due to the possibility of allylic rearrangement which gives additional analytical probe not available for other systems [Hughes (1941); Raber et al. (1974)]. Pioneering research of Goering et al. (1971) on the solvolyses of optically active allyl derivatives provided lots of information about ion-pairing in S_N1 solvolyses (Goering et al., 1971), however, due to the lack of analytical methods available during Goering's time, many questions about ion pair dynamics and stereochemistry of allylic rearrangements remained open. As modern analytical techniques such as chiral HPLC and laser-flash photolysis give unprecedented insights in the reaction kinetics, we decided to reconsider the problem of stereochemistry of allylic rearrangements. The title compound (R,E)-3-(4-chlorophenyl)-1-phenylallyl 4-nitrobenzoate was chosen as a model compound for this research, as all eight compounds which can be present in the system during its solvolysis in aqueous solvents (i.e. (R) and (S) isomers of title compound, (<I>E)-1-(4-chlorophenyl)-3-phenylallyl 4-nitrobenzoate, 3-(4-chlorophenyl)-1-phenylprop-2-en-1-ol, and 1-(4-chlorophenyl)-3-phenylprop-2-en-1-ol)) can be resolved using chiral HPLC. X-ray diffraction analysis was used to confirm the absolute configuration of the title compound (I).

The asymmetric unit contains one molecule of the title compound (I) which is shown in Figure 1. The plane defined by C4, C7, C8 and C9 (contains the allyl group) is not exactly coplanar with the adjacent chlorophenyl moiety (dihedral angle 9.71 (17)°). A deviation of coplanarity of a similar magnitude (6.5 (3)°) is observed in a related structure with a phenyl group as adjacent moiety [Cao et al. 2011)], while a less deviation (dihedral angle 1.7 (6)°) is observed in a related structure with a p-toluyl group as adjacent moiety [Wang et al. (2009)]. A slight deviation from coplanarity is observed in the nitrobenzoate group as well. The plane of the nitro group is almost coplanar with the phenyl ring enclosing a dihedral angle of 0.9 (2)°. However, the plane of the CO₂ group forms a dihedral angle of 10.16 (19)° with the phenyl ring.

The packing of (I) is shown in Figure 2. π-stacking is established between the chlorophenyl and nitrobenzoate moieties. These planes are arranged almost parallel to the viewing direction of Figure 2. A C-H···π contact is noted between C12-H12 and the nitrobenzoate moiety (distance C12···Cg 3.807 (2) Å). A weak C–H···O hydrogen bond is formed between C2 and O4 with a donor-acceptor distance of 3.529 (2) Å linking the molecules along [100] (see Fig. 3).

Related literature top

For background to the stereochemistry of allylic rearrangements, see: Hughes (1941); Raber et al. (1974); Goering et al. (1971). For details of the synthesis, see: Troshin et al. (2011); Gao et al. (1987); Roos & Donovan (1996). For related structures, see: Cao et al. (2011); Wang et al. (2009).

Experimental top

A four step synthesis was used to obtain the title compound (I).

1) (E)-3-(4-Chlorophenyl)-1-phenyl-prop-2-enone (18.1 g, 74.7 mmol, 87.2%) was synthesized from acetophenone (10.3 g, 85.7 mmol) and 4-chlorobenzaldehyde (12.0 g, 85.7 mmol) using an aldol condensation [Troshin et al. (2011)].

2) (E)-3-(4-Chlorophenyl)-1-phenyl-prop-2-enone (16.6 g, 68.4 mmol) was reduced with sodium borohydride (ca 5.0 g, ca 140 mmol) yielding the racemic (E)-3-(4-Chlorophenyl)-1-phenyl-prop-2-en-1-ol (15.7 g, 64.2 mmol, 94%) [Troshin et al. (2011)].

3) The (R) isomer of (E)-3-(4-Chlorophenyl)-1-phenyl-prop-2-en-1-ol was obtained by a Sharpless epoxidation of racemic (E)-3-(4-Chlorophenyl)-1-phenyl-prop-2-en-1-ol (15.5 g, 63.3 mmol) with D(-)-DIPT (1.78 g, 7.60 mmol), titanium(IV)isopropoxide (1.81 g, 6.33 mmol), and ^tBuOOH (8.4 ml of the 4.9 M CH₂Cl₂ solution [Gao et al. (1987)], 41.1 mmol) [Roos et al. (1996)]. The crude mixture was separated from the solvents and dissolved in ethanol followed by addition of piperidine (6.3 ml, 5.4 g, 64 mmol) and then refluxed for 10 h. The resulting solution was washed with 0.2 M aq HCl and water and then purified using column chromatography (silica gel, isohexane/diethyl ether) yielding R,E)-3-(4-Chlorophenyl)-1-phenyl-prop-2-en-1-ol (4.65 g, 19.0 mmol, 30%).

4) R,E)-3-(4-Chlorophenyl)-1-phenyl-prop-2-en-1-ol (3.00 g, 12.3 mmol) was dissolved in dichloromethane followed by addition of triethylamine (2.7 ml, 2.0 g, 19 mmol), DMAP (195 mg, 1.60 mmol), and 4-nitrobenzoyl chloride (2.96 g, 15.9 mmol) and the resulting solution was stirred for 30 min. The reaction mixture was washed with 0.2 M aq HCl and water, separated from the solvent, and the crude product was recrystallized twice from dichloromethane/pentane yielding (I) (1.90 g, 4.82 mmol, 39.4%) of > 99% ee (HPLC).

Structure description top

For background to the stereochemistry of allylic rearrangements, see: Hughes (1941); Raber et al. (1974); Goering et al. (1971). For details of the synthesis, see: Troshin et al. (2011); Gao et al. (1987); Roos & Donovan (1996). For related structures, see: Cao et al. (2011); Wang et al. (2009).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
	Fig. 2. The packing of the title compound viewed along [0 - 1 0].
	Fig. 3. Weak C–H···O contacts linking the molecules along [100].

(R,E)-3-(4-Chlorophenyl)-1-phenylallyl 4-nitrobenzoate top

Crystal data top

C₂₂H₁₆ClNO₄	F(000) = 816
M_r = 393.82	D_x = 1.38 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6811 reflections
a = 8.3817 (1) Å	θ = 3.1–27.5°
b = 9.9238 (2) Å	µ = 0.23 mm⁻¹
c = 22.8090 (4) Å	T = 173 K
V = 1897.21 (6) Å³	Block, colourless
Z = 4	0.28 × 0.15 × 0.13 mm

Data collection top

Nonius KappaCCD diffractometer	3847 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.030
MONTEL, graded multilayered X-ray optics monochromator	θ_max = 27.5°, θ_min = 3.2°
Detector resolution: 9 pixels mm^-1	h = −10→10
CCD; rotation images; thick slices scans	k = −12→11
12403 measured reflections	l = −29→28
4331 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.039P)² + 0.3359P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4331 reflections	Δρ_max = 0.17 e Å⁻³
253 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1854 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (5)

Crystal data top

C₂₂H₁₆ClNO₄	V = 1897.21 (6) Å³
M_r = 393.82	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.3817 (1) Å	µ = 0.23 mm⁻¹
b = 9.9238 (2) Å	T = 173 K
c = 22.8090 (4) Å	0.28 × 0.15 × 0.13 mm

Data collection top

Nonius KappaCCD diffractometer	3847 reflections with I > 2σ(I)
12403 measured reflections	R_int = 0.030
4331 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 0.17 e Å⁻³
S = 1.03	Δρ_min = −0.19 e Å⁻³
4331 reflections	Absolute structure: Flack (1983), 1854 Friedel pairs
253 parameters	Absolute structure parameter: 0.01 (5)
0 restraints

Special details top

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 > 2σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	1.05905 (6)	−0.23586 (5)	0.67154 (2)	0.04970 (13)
O1	1.0670 (2)	−0.12603 (15)	0.07501 (6)	0.0654 (4)
O2	1.1347 (2)	0.07816 (17)	0.05567 (6)	0.0674 (4)
O3	0.69865 (12)	0.07772 (10)	0.32577 (5)	0.0306 (2)
O4	0.72705 (18)	0.29656 (12)	0.30153 (5)	0.0476 (3)
N1	1.0677 (2)	−0.00643 (17)	0.08602 (6)	0.0456 (4)
C1	0.9715 (2)	−0.14740 (16)	0.61393 (7)	0.0348 (4)
C2	0.9926 (2)	−0.01089 (18)	0.61008 (8)	0.0433 (4)
H2	1.0551	0.0358	0.6383	0.052*
C3	0.9209 (2)	0.05778 (18)	0.56419 (7)	0.0423 (4)
H3	0.9343	0.1526	0.5614	0.051*
C4	0.82999 (18)	−0.00806 (16)	0.52214 (7)	0.0308 (3)
C5	0.8104 (2)	−0.14624 (17)	0.52765 (8)	0.0403 (4)
H5	0.7480	−0.1936	0.4996	0.048*
C6	0.8806 (2)	−0.21628 (17)	0.57359 (8)	0.0441 (4)
H6	0.8662	−0.3109	0.5771	0.053*
C7	0.75987 (18)	0.07074 (16)	0.47422 (7)	0.0317 (3)
H7	0.7667	0.1660	0.4776	0.038*
C8	0.68791 (18)	0.02343 (16)	0.42667 (7)	0.0304 (3)
H8	0.6799	−0.0714	0.4218	0.036*
C9	0.61891 (17)	0.11246 (16)	0.38042 (6)	0.0289 (3)
H9	0.6421	0.2087	0.3903	0.035*
C10	0.43980 (17)	0.09433 (14)	0.37273 (6)	0.0284 (3)
C11	0.36984 (18)	0.08652 (17)	0.31807 (7)	0.0357 (4)
H11	0.4345	0.0910	0.2839	0.043*
C12	0.2058 (2)	0.07210 (19)	0.31259 (8)	0.0441 (4)
H12	0.1587	0.0677	0.2748	0.053*
C13	0.11123 (19)	0.06417 (19)	0.36165 (9)	0.0438 (4)
H13	−0.0009	0.0534	0.3578	0.053*
C14	0.1797 (2)	0.07192 (18)	0.41646 (8)	0.0409 (4)
H14	0.1145	0.0669	0.4505	0.049*
C15	0.34379 (19)	0.08698 (16)	0.42224 (7)	0.0335 (3)
H15	0.3904	0.0923	0.4601	0.040*
C16	0.74556 (18)	0.17917 (16)	0.29088 (7)	0.0308 (3)
C17	0.82662 (18)	0.12685 (16)	0.23721 (6)	0.0294 (3)
C18	0.8264 (2)	−0.00856 (17)	0.22281 (7)	0.0377 (4)
H18	0.7725	−0.0714	0.2472	0.045*
C19	0.9049 (2)	−0.05269 (17)	0.17272 (8)	0.0417 (4)
H19	0.9046	−0.1453	0.1621	0.050*
C20	0.98271 (19)	0.04050 (17)	0.13903 (7)	0.0354 (4)
C21	0.9847 (2)	0.17555 (18)	0.15197 (8)	0.0440 (4)
H21	1.0391	0.2378	0.1275	0.053*
C22	0.9051 (2)	0.21839 (17)	0.20181 (7)	0.0412 (4)
H22	0.9045	0.3114	0.2117	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0626 (3)	0.0493 (2)	0.0372 (2)	0.0150 (2)	−0.0132 (2)	−0.00003 (18)
O1	0.0983 (12)	0.0535 (8)	0.0444 (8)	0.0182 (9)	0.0219 (8)	−0.0061 (6)
O2	0.0855 (11)	0.0720 (10)	0.0446 (8)	−0.0062 (9)	0.0325 (7)	−0.0015 (7)
O3	0.0303 (5)	0.0345 (6)	0.0270 (5)	0.0005 (5)	0.0067 (4)	−0.0003 (5)
O4	0.0703 (9)	0.0339 (6)	0.0387 (7)	0.0041 (6)	0.0168 (6)	−0.0010 (5)
N1	0.0510 (9)	0.0568 (10)	0.0289 (7)	0.0100 (8)	0.0067 (7)	−0.0020 (7)
C1	0.0376 (9)	0.0380 (8)	0.0288 (8)	0.0088 (7)	−0.0014 (6)	−0.0007 (6)
C2	0.0531 (11)	0.0413 (9)	0.0356 (9)	−0.0003 (8)	−0.0154 (8)	−0.0076 (7)
C3	0.0562 (11)	0.0324 (8)	0.0384 (9)	−0.0044 (8)	−0.0105 (8)	−0.0031 (7)
C4	0.0298 (7)	0.0356 (8)	0.0269 (7)	−0.0018 (7)	0.0005 (6)	−0.0023 (6)
C5	0.0466 (10)	0.0359 (9)	0.0386 (9)	−0.0052 (8)	−0.0135 (8)	−0.0055 (7)
C6	0.0556 (11)	0.0310 (8)	0.0458 (10)	−0.0002 (8)	−0.0129 (8)	−0.0007 (7)
C7	0.0311 (7)	0.0333 (8)	0.0305 (7)	−0.0013 (7)	−0.0004 (6)	−0.0011 (6)
C8	0.0284 (7)	0.0324 (8)	0.0303 (8)	−0.0001 (6)	0.0011 (6)	−0.0013 (6)
C9	0.0289 (7)	0.0346 (8)	0.0231 (7)	−0.0001 (6)	0.0036 (5)	−0.0029 (6)
C10	0.0287 (7)	0.0257 (7)	0.0309 (7)	0.0023 (6)	0.0020 (6)	−0.0005 (5)
C11	0.0338 (8)	0.0436 (9)	0.0297 (8)	0.0014 (7)	0.0005 (6)	0.0013 (7)
C12	0.0356 (9)	0.0536 (11)	0.0430 (10)	0.0005 (9)	−0.0097 (7)	0.0026 (8)
C13	0.0278 (8)	0.0453 (10)	0.0583 (12)	0.0016 (7)	−0.0014 (8)	0.0037 (9)
C14	0.0332 (8)	0.0429 (9)	0.0466 (10)	0.0031 (8)	0.0119 (7)	0.0015 (8)
C15	0.0356 (8)	0.0369 (8)	0.0281 (8)	0.0008 (7)	0.0047 (6)	0.0007 (6)
C16	0.0301 (8)	0.0358 (8)	0.0265 (7)	0.0014 (6)	0.0001 (6)	0.0029 (6)
C17	0.0269 (7)	0.0356 (8)	0.0258 (7)	0.0036 (6)	−0.0006 (6)	0.0019 (6)
C18	0.0424 (9)	0.0363 (8)	0.0344 (9)	−0.0009 (8)	0.0073 (7)	0.0014 (7)
C19	0.0536 (10)	0.0361 (8)	0.0352 (9)	0.0026 (8)	0.0067 (8)	−0.0027 (7)
C20	0.0354 (8)	0.0467 (9)	0.0239 (7)	0.0081 (7)	0.0038 (6)	0.0011 (6)
C21	0.0538 (11)	0.0435 (9)	0.0348 (9)	−0.0023 (8)	0.0129 (8)	0.0045 (7)
C22	0.0542 (10)	0.0350 (9)	0.0343 (9)	−0.0004 (8)	0.0107 (8)	0.0019 (7)

Geometric parameters (Å, º) top

Cl1—C1	1.7424 (16)	C9—H9	1.0000
O1—N1	1.213 (2)	C10—C11	1.380 (2)
O2—N1	1.224 (2)	C10—C15	1.389 (2)
O3—C16	1.3422 (18)	C11—C12	1.388 (2)
O3—C9	1.4557 (17)	C11—H11	0.9500
O4—C16	1.200 (2)	C12—C13	1.373 (3)
N1—C20	1.479 (2)	C12—H12	0.9500
C1—C2	1.369 (2)	C13—C14	1.378 (3)
C1—C6	1.376 (2)	C13—H13	0.9500
C2—C3	1.386 (2)	C14—C15	1.389 (2)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.388 (2)	C15—H15	0.9500
C3—H3	0.9500	C16—C17	1.493 (2)
C4—C5	1.387 (2)	C17—C22	1.382 (2)
C4—C7	1.467 (2)	C17—C18	1.383 (2)
C5—C6	1.389 (2)	C18—C19	1.389 (2)
C5—H5	0.9500	C18—H18	0.9500
C6—H6	0.9500	C19—C20	1.368 (2)
C7—C8	1.327 (2)	C19—H19	0.9500
C7—H7	0.9500	C20—C21	1.372 (2)
C8—C9	1.493 (2)	C21—C22	1.385 (2)
C8—H8	0.9500	C21—H21	0.9500
C9—C10	1.522 (2)	C22—H22	0.9500

C16—O3—C9	117.68 (12)	C10—C11—C12	120.54 (15)
O1—N1—O2	123.77 (16)	C10—C11—H11	119.7
O1—N1—C20	118.37 (15)	C12—C11—H11	119.7
O2—N1—C20	117.86 (16)	C13—C12—C11	120.26 (16)
C2—C1—C6	121.35 (16)	C13—C12—H12	119.9
C2—C1—Cl1	119.49 (13)	C11—C12—H12	119.9
C6—C1—Cl1	119.15 (13)	C12—C13—C14	119.71 (15)
C1—C2—C3	118.60 (16)	C12—C13—H13	120.1
C1—C2—H2	120.7	C14—C13—H13	120.1
C3—C2—H2	120.7	C13—C14—C15	120.30 (16)
C2—C3—C4	121.90 (16)	C13—C14—H14	119.8
C2—C3—H3	119.1	C15—C14—H14	119.8
C4—C3—H3	119.1	C10—C15—C14	120.13 (15)
C5—C4—C3	117.89 (15)	C10—C15—H15	119.9
C5—C4—C7	123.18 (15)	C14—C15—H15	119.9
C3—C4—C7	118.93 (14)	O4—C16—O3	124.77 (14)
C4—C5—C6	120.87 (15)	O4—C16—C17	124.22 (14)
C4—C5—H5	119.6	O3—C16—C17	111.01 (13)
C6—C5—H5	119.6	C22—C17—C18	120.02 (15)
C1—C6—C5	119.38 (16)	C22—C17—C16	117.84 (14)
C1—C6—H6	120.3	C18—C17—C16	122.14 (14)
C5—C6—H6	120.3	C17—C18—C19	120.07 (15)
C8—C7—C4	127.06 (15)	C17—C18—H18	120.0
C8—C7—H7	116.5	C19—C18—H18	120.0
C4—C7—H7	116.5	C20—C19—C18	118.33 (15)
C7—C8—C9	122.99 (15)	C20—C19—H19	120.8
C7—C8—H8	118.5	C18—C19—H19	120.8
C9—C8—H8	118.5	C19—C20—C21	123.05 (15)
O3—C9—C8	106.69 (12)	C19—C20—N1	118.43 (15)
O3—C9—C10	109.04 (12)	C21—C20—N1	118.53 (15)
C8—C9—C10	113.18 (13)	C20—C21—C22	118.06 (16)
O3—C9—H9	109.3	C20—C21—H21	121.0
C8—C9—H9	109.3	C22—C21—H21	121.0
C10—C9—H9	109.3	C17—C22—C21	120.47 (16)
C11—C10—C15	119.05 (13)	C17—C22—H22	119.8
C11—C10—C9	121.99 (13)	C21—C22—H22	119.8
C15—C10—C9	118.96 (13)

C6—C1—C2—C3	−0.3 (3)	C12—C13—C14—C15	−0.3 (3)
Cl1—C1—C2—C3	−179.48 (14)	C11—C10—C15—C14	0.0 (2)
C1—C2—C3—C4	−0.5 (3)	C9—C10—C15—C14	179.30 (15)
C2—C3—C4—C5	0.9 (3)	C13—C14—C15—C10	0.0 (3)
C2—C3—C4—C7	−178.96 (17)	C9—O3—C16—O4	0.3 (2)
C3—C4—C5—C6	−0.5 (3)	C9—O3—C16—C17	179.34 (11)
C7—C4—C5—C6	179.38 (16)	O4—C16—C17—C22	9.7 (2)
C2—C1—C6—C5	0.7 (3)	O3—C16—C17—C22	−169.42 (14)
Cl1—C1—C6—C5	179.90 (14)	O4—C16—C17—C18	−171.07 (18)
C4—C5—C6—C1	−0.3 (3)	O3—C16—C17—C18	9.8 (2)
C5—C4—C7—C8	−9.2 (3)	C22—C17—C18—C19	−0.1 (3)
C3—C4—C7—C8	170.68 (15)	C16—C17—C18—C19	−179.32 (15)
C4—C7—C8—C9	179.48 (14)	C17—C18—C19—C20	0.7 (3)
C16—O3—C9—C8	−136.58 (13)	C18—C19—C20—C21	−1.0 (3)
C16—O3—C9—C10	100.86 (15)	C18—C19—C20—N1	179.41 (15)
C7—C8—C9—O3	121.40 (15)	O1—N1—C20—C19	−1.1 (3)
C7—C8—C9—C10	−118.67 (16)	O2—N1—C20—C19	178.82 (17)
O3—C9—C10—C11	−17.5 (2)	O1—N1—C20—C21	179.29 (18)
C8—C9—C10—C11	−136.06 (15)	O2—N1—C20—C21	−0.8 (3)
O3—C9—C10—C15	163.25 (13)	C19—C20—C21—C22	0.6 (3)
C8—C9—C10—C15	44.68 (19)	N1—C20—C21—C22	−179.82 (16)
C15—C10—C11—C12	0.3 (3)	C18—C17—C22—C21	−0.3 (3)
C9—C10—C11—C12	−178.98 (16)	C16—C17—C22—C21	178.93 (16)
C10—C11—C12—C13	−0.6 (3)	C20—C21—C22—C17	0.1 (3)
C11—C12—C13—C14	0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.95	2.59	3.529 (2)	168
C12—H12···Cgⁱⁱ	0.95	2.92	3.8072 (19)	157

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

Experimental details

Crystal data
Chemical formula	C₂₂H₁₆ClNO₄
M_r	393.82
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	8.3817 (1), 9.9238 (2), 22.8090 (4)
V (Å³)	1897.21 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.28 × 0.15 × 0.13

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12403, 4331, 3847
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.083, 1.03
No. of reflections	4331
No. of parameters	253
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19
Absolute structure	Flack (1983), 1854 Friedel pairs
Absolute structure parameter	0.01 (5)

Computer programs: COLLECT (Hooft, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.95	2.59	3.529 (2)	168
C12—H12···Cgⁱⁱ	0.95	2.92	3.8072 (19)	157

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

Acknowledgements

The authors thank Professor Peter Klüfers for generous allocation of diffractometer time.

References

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