(R,E)-3-(4-Chloro-phen-yl)-1-phenyl-allyl 4-nitro-benzoate.

The title compound, C(22)H(16)ClNO(4), adopts a conformation in which the phenyl ring plane forms similar dihedral angles with the nitro-benzoate C(6) ring [76.97 (8)°] and the chloro-phenyl group [76.95 (8)°]; the dihedral angle between the chloro-phenyl and nitro-benzoate 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, mol-ecules 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 = 393.82

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.083

S = 1.03

4331 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.19 e Å−3

Absolute structure: Flack (1983) ▶, 1854 Friedel pairs

Flack parameter: 0.01 (5)

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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032813/gg2092sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032813/gg2092Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812032813/gg2092Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H16ClNO4	F(000) = 816
Mr = 393.82	Dx = 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

Nonius KappaCCD diffractometer	3847 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.030
MONTEL, graded multilayered X-ray optics monochromator	θmax = 27.5°, θmin = 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 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(Fo2) + (0.039P)2 + 0.3359P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
4331 reflections	Δρmax = 0.17 e Å−3
253 parameters	Δρmin = −0.19 e Å−3
0 restraints	Absolute structure: Flack (1983), 1854 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (5)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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⋯Cg ii	0.95	2.92	3.8072 (19)	157

Symmetry codes: (i) ; (ii) .