(E)-Phenethyl 3-(3,4-dihydr­oxy-5-nitro­phen­yl)acrylate

Xia, C.-N.; Hu, W.-X.; Zhou, W.

doi:10.1107/S160053680705859X

(E)-Phenethyl 3-(3,4-dihydroxy-5-nitrophenyl)acrylate

The title compound, also known as 5-nitrocaffeic acid phenethyl ester, C₁₇H₁₅NO₆, was prepared by the condensation reaction of 3,4-dihydroxy-5-nitrobenzaldehyde, Meldrum's acid and 2-phenylethanol. The dihedral angle between the phenyl and benzene rings is 78.12 (5)°. Inter- and intramolecular hydrogen bonds help to stabilize the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705859X/wn2218sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680705859X/wn2218Isup2.hkl Contains datablock I

CCDC reference: 673003

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.002 Å
R factor = 0.043
wR factor = 0.124
Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       2.88 Sigma
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C3      ..       7.00 su

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

Comment top

Caffeic acid and its derivatives are widely distributed in the plant kingdom (Chen et al., 1999). The compounds are known to have anti-atherosclerotic, antibacterial, anti-inflammatory, antiproliferative, immunostimulatory, anti-oxidative, antiviral, and neuroprotective properties (Son et al., 2002). In a continuation of our work on the structure-activity relationship of caffeic acid derivatives, we have obtained, by a one-pot method (Hu et al., 2006), the title compound, 5-nitroCAPE, as light brown crystals.

The molecular structure of 5-nitroCAPE is illustrated in Fig. 1. The molecule displays an E configuration, with the benzene ring and carboxylate group located on opposite sides of the C7═C8 double bond. The bond lengths and angles are similar to those of caffeic acid phenethyl ester (CAPE), reported by Son et al. (2001). Atoms C1—C9, N1 and O1—O5 are essentially coplanar, with a mean deviation from the least-squares plane of 0.052 (1) Å; atom C10 deviates from this plane by 0.211 (2) Å. The crystal packing (Fig. 2) is stabilized by intramolecular O—H···O and O—H···N hydrogen bonds; the crystal structure also involves intermolecular C—H···O hydrogen bonds (Table 1). The molecules of 5-nitroCAPE form stacks along the b axis in a head-to-tail manner forming a dimeric structure; this differs from the head-to-head stacking found in CAPE.

Related literature top

For related literature, see: Chen et al. (1999); Hu et al. (2006); Son & Lewis (2002); Son et al. (2001).

Experimental top

5-NitroCAPE was obtained by the method of Hu et al. (2006). Crystals suitable for structure analysis were obtained by slow evaporation of a solution of a mixture of tetrahydrofuran and acetone (2:1, v/v) as light brown crystalline prisms.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of 5-nitroCAPE, shown with 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of 5-nitroCAPE, viewed along the b axis. Dashed lines indicate hydrogen bonds.

(E)-Phenethyl 3-(3,4-dihydroxy-5-nitrophenyl)acrylate top

Crystal data top

C₁₇H₁₅NO₆	F(000) = 688
M_r = 329.30	D_x = 1.400 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2071 reflections
a = 8.5840 (17) Å	θ = 2.4–24.2°
b = 5.3725 (11) Å	µ = 0.11 mm⁻¹
c = 33.904 (7) Å	T = 296 K
β = 91.757 (3)°	Prismatic, light brown
V = 1562.8 (5) Å³	0.25 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3509 independent reflections
Radiation source: fine-focus sealed tube	2268 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→6
T_min = 0.974, T_max = 0.986	k = −6→6
9258 measured reflections	l = −43→43

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0543P)² + 0.128P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3509 reflections	Δρ_max = 0.16 e Å⁻³
226 parameters	Δρ_min = −0.16 e Å⁻³
3 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0046 (16)

Crystal data top

C₁₇H₁₅NO₆	V = 1562.8 (5) Å³
M_r = 329.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5840 (17) Å	µ = 0.11 mm⁻¹
b = 5.3725 (11) Å	T = 296 K
c = 33.904 (7) Å	0.25 × 0.20 × 0.10 mm
β = 91.757 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3509 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2268 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.986	R_int = 0.026
9258 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	3 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.16 e Å⁻³
3509 reflections	Δρ_min = −0.16 e Å⁻³
226 parameters

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 > 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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.02260 (16)	1.0979 (2)	−0.05897 (4)	0.0718 (4)
O2	0.95350 (17)	1.0519 (2)	−0.12012 (4)	0.0732 (4)
O3	0.76239 (17)	0.7050 (3)	−0.14242 (3)	0.0665 (4)
H3X	0.826 (2)	0.831 (3)	−0.1453 (6)	0.088 (7)*
O4	0.59294 (16)	0.3310 (3)	−0.12109 (3)	0.0649 (4)
H4X	0.538 (2)	0.223 (4)	−0.1112 (6)	0.085 (7)*
O5	0.57612 (18)	0.0167 (3)	0.08346 (3)	0.0802 (5)
O6	0.73569 (15)	0.3321 (2)	0.09845 (3)	0.0581 (3)
N1	0.94801 (17)	0.9898 (3)	−0.08490 (4)	0.0550 (4)
C1	0.75303 (18)	0.5211 (3)	−0.02353 (4)	0.0439 (4)
C2	0.84387 (18)	0.7183 (3)	−0.03486 (4)	0.0461 (4)
H2	0.9009	0.8087	−0.0160	0.055*
C3	0.85022 (18)	0.7820 (3)	−0.07455 (4)	0.0445 (4)
C4	0.76560 (19)	0.6537 (3)	−0.10382 (4)	0.0464 (4)
C5	0.67344 (18)	0.4518 (3)	−0.09193 (4)	0.0466 (4)
C6	0.66815 (18)	0.3901 (3)	−0.05288 (4)	0.0466 (4)
H6	0.6063	0.2568	−0.0455	0.056*
C7	0.74503 (18)	0.4516 (3)	0.01813 (4)	0.0481 (4)
H7	0.7963	0.5539	0.0365	0.058*
C8	0.6712 (2)	0.2558 (3)	0.03185 (4)	0.0545 (4)
H8	0.6240	0.1503	0.0133	0.065*
C9	0.6564 (2)	0.1890 (3)	0.07324 (4)	0.0535 (4)
C10	0.7142 (2)	0.2802 (3)	0.14011 (4)	0.0560 (5)
H10A	0.7480	0.1120	0.1464	0.067*
H10B	0.6051	0.2955	0.1463	0.067*
C11	0.8094 (2)	0.4642 (4)	0.16361 (4)	0.0614 (5)
H11A	0.7801	0.6320	0.1559	0.074*
H11B	0.9190	0.4416	0.1584	0.074*
C12	0.7826 (2)	0.4277 (3)	0.20708 (4)	0.0518 (4)
C13	0.6843 (2)	0.5827 (4)	0.22689 (5)	0.0674 (5)
H13	0.6373	0.7156	0.2136	0.081*
C14	0.6541 (3)	0.5445 (4)	0.26612 (6)	0.0820 (7)
H14	0.5878	0.6519	0.2791	0.098*
C15	0.7209 (3)	0.3504 (4)	0.28595 (5)	0.0778 (6)
H15	0.6997	0.3239	0.3124	0.093*
C16	0.8195 (3)	0.1940 (4)	0.26687 (6)	0.0781 (6)
H16	0.8659	0.0613	0.2804	0.094*
C17	0.8500 (2)	0.2332 (4)	0.22766 (5)	0.0674 (5)
H17	0.9173	0.1263	0.2149	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0780 (9)	0.0685 (9)	0.0685 (8)	−0.0313 (7)	−0.0021 (7)	−0.0013 (6)
O2	0.0860 (9)	0.0773 (9)	0.0565 (7)	−0.0254 (8)	0.0078 (7)	0.0172 (6)
O3	0.0834 (10)	0.0783 (9)	0.0378 (6)	−0.0229 (8)	0.0016 (6)	0.0106 (6)
O4	0.0823 (9)	0.0784 (9)	0.0338 (6)	−0.0338 (8)	−0.0015 (6)	−0.0013 (6)
O5	0.1063 (11)	0.0848 (9)	0.0495 (7)	−0.0534 (9)	0.0003 (7)	0.0065 (6)
O6	0.0772 (8)	0.0644 (8)	0.0328 (5)	−0.0260 (6)	0.0032 (5)	−0.0010 (5)
N1	0.0568 (9)	0.0536 (8)	0.0549 (8)	−0.0082 (7)	0.0065 (7)	0.0045 (7)
C1	0.0467 (9)	0.0500 (9)	0.0350 (7)	−0.0057 (7)	0.0024 (6)	−0.0028 (6)
C2	0.0484 (9)	0.0505 (9)	0.0396 (8)	−0.0078 (8)	0.0007 (7)	−0.0044 (7)
C3	0.0446 (9)	0.0452 (9)	0.0440 (8)	−0.0079 (7)	0.0057 (7)	0.0019 (7)
C4	0.0498 (9)	0.0538 (10)	0.0359 (8)	−0.0032 (8)	0.0043 (7)	0.0024 (7)
C5	0.0512 (9)	0.0531 (9)	0.0356 (8)	−0.0085 (8)	0.0013 (7)	−0.0028 (7)
C6	0.0510 (9)	0.0499 (9)	0.0389 (8)	−0.0115 (8)	0.0037 (7)	0.0007 (7)
C7	0.0528 (10)	0.0554 (10)	0.0362 (8)	−0.0103 (8)	0.0017 (7)	−0.0047 (7)
C8	0.0662 (11)	0.0606 (10)	0.0365 (8)	−0.0194 (9)	−0.0004 (7)	−0.0036 (7)
C9	0.0624 (11)	0.0579 (10)	0.0400 (8)	−0.0158 (9)	0.0011 (8)	0.0003 (7)
C10	0.0725 (12)	0.0637 (11)	0.0318 (8)	−0.0157 (9)	0.0033 (7)	0.0045 (7)
C11	0.0797 (13)	0.0640 (11)	0.0406 (9)	−0.0193 (10)	0.0048 (8)	−0.0016 (8)
C12	0.0616 (11)	0.0551 (10)	0.0386 (8)	−0.0129 (9)	−0.0006 (7)	−0.0033 (7)
C13	0.0867 (14)	0.0624 (12)	0.0532 (10)	0.0046 (11)	0.0041 (10)	0.0006 (9)
C14	0.1038 (17)	0.0859 (15)	0.0573 (12)	0.0011 (13)	0.0190 (11)	−0.0158 (11)
C15	0.0981 (16)	0.0972 (16)	0.0382 (9)	−0.0266 (14)	0.0022 (10)	−0.0002 (10)
C16	0.0931 (16)	0.0859 (15)	0.0542 (11)	−0.0053 (13)	−0.0156 (11)	0.0169 (11)
C17	0.0723 (13)	0.0701 (13)	0.0598 (11)	0.0063 (10)	0.0004 (9)	0.0009 (9)

Geometric parameters (Å, º) top

O1—N1	1.2189 (17)	C7—H7	0.9300
O2—N1	1.2420 (17)	C8—C9	1.458 (2)
O3—C4	1.3366 (18)	C8—H8	0.9300
O3—H3X	0.878 (15)	C10—C11	1.496 (2)
O4—C5	1.3544 (18)	C10—H10A	0.9700
O4—H4X	0.826 (15)	C10—H10B	0.9700
O5—C9	1.2105 (19)	C11—C12	1.511 (2)
O6—C9	1.3227 (19)	C11—H11A	0.9700
O6—C10	1.4569 (16)	C11—H11B	0.9700
N1—C3	1.447 (2)	C12—C17	1.374 (2)
C1—C2	1.377 (2)	C12—C13	1.375 (2)
C1—C6	1.404 (2)	C13—C14	1.378 (2)
C1—C7	1.465 (2)	C13—H13	0.9300
C2—C3	1.391 (2)	C14—C15	1.358 (3)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.394 (2)	C15—C16	1.369 (3)
C4—C5	1.408 (2)	C15—H15	0.9300
C5—C6	1.367 (2)	C16—C17	1.379 (2)
C6—H6	0.9300	C16—H16	0.9300
C7—C8	1.320 (2)	C17—H17	0.9300

C4—O3—H3X	105.9 (14)	O6—C9—C8	114.86 (14)
C5—O4—H4X	109.0 (14)	O6—C10—C11	107.86 (13)
C9—O6—C10	115.93 (12)	O6—C10—H10A	110.1
O1—N1—O2	122.06 (14)	C11—C10—H10A	110.1
O1—N1—C3	119.26 (13)	O6—C10—H10B	110.1
O2—N1—C3	118.68 (14)	C11—C10—H10B	110.1
C2—C1—C6	118.29 (13)	H10A—C10—H10B	108.4
C2—C1—C7	120.60 (14)	C10—C11—C12	109.68 (14)
C6—C1—C7	121.11 (14)	C10—C11—H11A	109.7
C1—C2—C3	119.89 (14)	C12—C11—H11A	109.7
C1—C2—H2	120.1	C10—C11—H11B	109.7
C3—C2—H2	120.1	C12—C11—H11B	109.7
C2—C3—C4	122.14 (14)	H11A—C11—H11B	108.2
C2—C3—N1	117.69 (14)	C17—C12—C13	117.88 (15)
C4—C3—N1	120.17 (13)	C17—C12—C11	121.29 (16)
O3—C4—C3	126.12 (14)	C13—C12—C11	120.77 (16)
O3—C4—C5	116.37 (14)	C12—C13—C14	121.15 (19)
C3—C4—C5	117.51 (13)	C12—C13—H13	119.4
O4—C5—C6	124.00 (14)	C14—C13—H13	119.4
O4—C5—C4	116.01 (13)	C15—C14—C13	120.2 (2)
C6—C5—C4	119.99 (14)	C15—C14—H14	119.9
C5—C6—C1	122.18 (14)	C13—C14—H14	119.9
C5—C6—H6	118.9	C14—C15—C16	119.68 (18)
C1—C6—H6	118.9	C14—C15—H15	120.2
C8—C7—C1	125.48 (15)	C16—C15—H15	120.2
C8—C7—H7	117.3	C15—C16—C17	120.0 (2)
C1—C7—H7	117.3	C15—C16—H16	120.0
C7—C8—C9	126.34 (15)	C17—C16—H16	120.0
C7—C8—H8	116.8	C12—C17—C16	121.07 (19)
C9—C8—H8	116.8	C12—C17—H17	119.5
O5—C9—O6	123.07 (14)	C16—C17—H17	119.5
O5—C9—C8	122.07 (15)

C6—C1—C2—C3	−0.3 (2)	C2—C1—C7—C8	−174.75 (17)
C7—C1—C2—C3	180.00 (15)	C6—C1—C7—C8	5.6 (3)
C1—C2—C3—C4	0.7 (2)	C1—C7—C8—C9	−177.28 (17)
C1—C2—C3—N1	−179.69 (14)	C10—O6—C9—O5	−3.5 (3)
O1—N1—C3—C2	1.2 (2)	C10—O6—C9—C8	175.86 (15)
O2—N1—C3—C2	−178.96 (15)	C7—C8—C9—O5	174.04 (19)
O1—N1—C3—C4	−179.13 (15)	C7—C8—C9—O6	−5.3 (3)
O2—N1—C3—C4	0.7 (2)	C9—O6—C10—C11	−178.53 (15)
C2—C3—C4—O3	178.60 (16)	O6—C10—C11—C12	176.41 (15)
N1—C3—C4—O3	−1.0 (3)	C10—C11—C12—C17	76.2 (2)
C2—C3—C4—C5	−0.9 (2)	C10—C11—C12—C13	−101.0 (2)
N1—C3—C4—C5	179.52 (14)	C17—C12—C13—C14	0.0 (3)
O3—C4—C5—O4	0.6 (2)	C11—C12—C13—C14	177.26 (18)
C3—C4—C5—O4	−179.90 (14)	C12—C13—C14—C15	−0.4 (3)
O3—C4—C5—C6	−178.84 (15)	C13—C14—C15—C16	0.6 (3)
C3—C4—C5—C6	0.7 (2)	C14—C15—C16—C17	−0.3 (3)
O4—C5—C6—C1	−179.71 (15)	C13—C12—C17—C16	0.3 (3)
C4—C5—C6—C1	−0.3 (3)	C11—C12—C17—C16	−176.97 (18)
C2—C1—C6—C5	0.1 (2)	C15—C16—C17—C12	−0.1 (3)
C7—C1—C6—C5	179.84 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3X···O2	0.88 (2)	1.81 (2)	2.5807 (19)	145 (2)
O3—H3X···N1	0.88 (2)	2.43 (2)	2.914 (2)	116 (2)
O4—H4X···O5ⁱ	0.83 (2)	1.89 (2)	2.7088 (18)	174 (2)
C6—H6···O5ⁱ	0.93	2.48	3.180 (2)	132
C7—H7···O1ⁱⁱ	0.93	2.54	3.404 (2)	156
C15—H15···O4ⁱⁱⁱ	0.93	2.60	3.507 (2)	166

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅NO₆
M_r	329.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.5840 (17), 5.3725 (11), 33.904 (7)
β (°)	91.757 (3)
V (Å³)	1562.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.974, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	9258, 3509, 2268
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.124, 1.06
No. of reflections	3509
No. of parameters	226
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2005), SHELXTL.