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The title compound, C20H17NO6, was synthesized by the reaction of syringaldehyde with hippuric acid. The mol­ecule adopts a Z configuration about the central olefinic bond. The two benzene rings and the oxazolone ring are almost coplanar. The crystal structure is stabilized by weak inter­molecular C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051458/hg2317sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051458/hg2317Isup2.hkl
Contains datablock I

CCDC reference: 667433

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • R factor = 0.040
  • wR factor = 0.117
  • Data-to-parameter ratio = 12.8

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Comment top

The title compound, (I), was prepared as part of our systematic search for organic functional materials with nonlinear optical properties (Sun & Cui, 2007). Oxazolones are highly versatile intermediates used for the synthesis of several biologically active organic molecules, such as amino acids, peptides, antimicrobial or antitumor compounds, immunomodulators, heterocyclic precursors for biosensors coupling, and photosensitive composition devices for proteins (Aaglawe et al., 2003; Grassi et al., 2004; Khan et al., 2006). Moreover, some of them are reported to exhibit promising nonlinear optical properties (Song et al., 2001).

The molecule of compound (I) possesses normal geometric parameters and adopts a Z configuration about the central olefinic bond (Fig. 1). The two phenyl rings and the oxazolone ring are almost coplanar which allows conjugation (Table 1). Also, while O4, O5, O6, C17 and C18 are approximately coplanar with their attached benzene ring, O3,C19 and C20 deviate from their mother benzene ring on the same side (Fig. 1;Table 1). The title compound shows a weak intermolecular hydrogen bond between the C8 and O1 atoms (C8—H8···O1i: C8—H8 = 0.93 Å, H8···O1 = 2.56 Å, C8···O1 = 3.483 (2) Å and C8—H8···O1 = 172 °; symmetry code: (i) 3 - x, 1 - y, 1 - z), which contribute to the crystal structure stabilization.

Similar structures have been observed in the related oxazolone analogues reported by Imhof & Garms (2005), Song et al. (2004), and Vasuki et al. (2001).

Related literature top

For background literature, see: Aaglawe et al. (2003); Grassi et al. (2004); Khan et al. (2006); Song et al. (2001); Sun & Cui (2007). For related structures, see: Imhof & Garms (2005); Song et al. (2004); Vasuki et al. (2001).

Experimental top

The title compound was synthesized from syringaldehyde and hippuric acid as reported (Song et al., 2001). A mixture of hippuric acid (2.2 mmol), syringaldehyde (2 mmol), sodium acetate (3 mmol) in acetic anhydride (8 ml) was refluxed for 5 hr. It was then cooled and ethanol (10 ml) was added it. The resulting mixture was left over night at room temp. The solid thus obtained was filtered, dried and crystallized from ethanol to get title compound (I) in 67% yield. A single-crystal suitable for an X-ray structural analysis was obtained by slowly evaporating from ethanol at room temperature.

Refinement top

All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.96 Å and Uiso(H) = 1.5Ueq(C). All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances 0.93 Å and Uiso(H) = 1.2Ueq(C).

Structure description top

The title compound, (I), was prepared as part of our systematic search for organic functional materials with nonlinear optical properties (Sun & Cui, 2007). Oxazolones are highly versatile intermediates used for the synthesis of several biologically active organic molecules, such as amino acids, peptides, antimicrobial or antitumor compounds, immunomodulators, heterocyclic precursors for biosensors coupling, and photosensitive composition devices for proteins (Aaglawe et al., 2003; Grassi et al., 2004; Khan et al., 2006). Moreover, some of them are reported to exhibit promising nonlinear optical properties (Song et al., 2001).

The molecule of compound (I) possesses normal geometric parameters and adopts a Z configuration about the central olefinic bond (Fig. 1). The two phenyl rings and the oxazolone ring are almost coplanar which allows conjugation (Table 1). Also, while O4, O5, O6, C17 and C18 are approximately coplanar with their attached benzene ring, O3,C19 and C20 deviate from their mother benzene ring on the same side (Fig. 1;Table 1). The title compound shows a weak intermolecular hydrogen bond between the C8 and O1 atoms (C8—H8···O1i: C8—H8 = 0.93 Å, H8···O1 = 2.56 Å, C8···O1 = 3.483 (2) Å and C8—H8···O1 = 172 °; symmetry code: (i) 3 - x, 1 - y, 1 - z), which contribute to the crystal structure stabilization.

Similar structures have been observed in the related oxazolone analogues reported by Imhof & Garms (2005), Song et al. (2004), and Vasuki et al. (2001).

For background literature, see: Aaglawe et al. (2003); Grassi et al. (2004); Khan et al. (2006); Song et al. (2001); Sun & Cui (2007). For related structures, see: Imhof & Garms (2005); Song et al. (2004); Vasuki et al. (2001).

Computing details top

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

Figures top
[Figure 1] Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii.
2,6-Dimethoxy-4-(5-oxo-2-phenyl-4,5-dihydro-1,3-oxazol-4-ylidenemethyl)phenyl acetate top
Crystal data top
C20H17NO6Z = 2
Mr = 367.35F(000) = 384
Triclinic, P1Dx = 1.350 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.8400 (13) ÅCell parameters from 2426 reflections
b = 10.4431 (15) Åθ = 2.0–28.2°
c = 10.9693 (16) ŵ = 0.10 mm1
α = 111.074 (6)°T = 273 K
β = 96.544 (6)°Block, red
γ = 102.119 (6)°0.15 × 0.12 × 0.10 mm
V = 903.7 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
3176 independent reflections
Radiation source: fine-focus sealed tube2244 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
φ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.985, Tmax = 0.990k = 1212
10391 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.117 w = 1/[σ2(Fo2) + (0.0571P)2 + 0.1424P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.009
3176 reflectionsΔρmax = 0.17 e Å3
248 parametersΔρmin = 0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.005 (2)
Crystal data top
C20H17NO6γ = 102.119 (6)°
Mr = 367.35V = 903.7 (2) Å3
Triclinic, P1Z = 2
a = 8.8400 (13) ÅMo Kα radiation
b = 10.4431 (15) ŵ = 0.10 mm1
c = 10.9693 (16) ÅT = 273 K
α = 111.074 (6)°0.15 × 0.12 × 0.10 mm
β = 96.544 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3176 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2244 reflections with I > 2σ(I)
Tmin = 0.985, Tmax = 0.990Rint = 0.028
10391 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 1.02Δρmax = 0.17 e Å3
3176 reflectionsΔρmin = 0.16 e Å3
248 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
xyzUiso*/Ueq
O11.19578 (16)0.71134 (16)0.39534 (16)0.0721 (4)
O21.22759 (14)0.50852 (13)0.41266 (13)0.0552 (4)
O30.2048 (2)0.1945 (2)0.11379 (17)0.0945 (6)
O40.41331 (15)0.10522 (14)0.14667 (14)0.0628 (4)
O50.30933 (16)0.51339 (15)0.12013 (15)0.0665 (4)
O60.21087 (14)0.24950 (15)0.10383 (13)0.0595 (4)
N10.97910 (17)0.36389 (15)0.32873 (14)0.0478 (4)
C11.1388 (2)0.5898 (2)0.3770 (2)0.0535 (5)
C20.9783 (2)0.49460 (19)0.32069 (18)0.0478 (4)
C31.1222 (2)0.37709 (19)0.37993 (17)0.0466 (4)
C41.1841 (2)0.2698 (2)0.40751 (18)0.0478 (4)
C51.0819 (2)0.1380 (2)0.3802 (2)0.0633 (6)
H50.97510.11920.34460.076*
C61.1380 (3)0.0351 (2)0.4056 (2)0.0733 (6)
H61.06910.05330.38700.088*
C71.2958 (3)0.0623 (3)0.4584 (2)0.0708 (6)
H71.33340.00740.47590.085*
C81.3972 (3)0.1921 (2)0.4852 (2)0.0675 (6)
H81.50390.21020.52060.081*
C91.3425 (2)0.2959 (2)0.4601 (2)0.0582 (5)
H91.41230.38390.47850.070*
C100.8562 (2)0.5342 (2)0.27495 (18)0.0501 (5)
H100.88080.62570.27600.060*
C110.6911 (2)0.45420 (19)0.22406 (17)0.0456 (4)
C120.5844 (2)0.5246 (2)0.19266 (18)0.0498 (5)
H120.62040.61800.20030.060*
C130.4248 (2)0.4545 (2)0.15007 (18)0.0492 (5)
C140.3728 (2)0.3144 (2)0.13583 (17)0.0477 (5)
C150.4782 (2)0.24279 (19)0.16484 (17)0.0463 (4)
C160.6370 (2)0.31274 (19)0.20929 (17)0.0471 (4)
H160.70830.26570.22950.057*
C170.3567 (3)0.6575 (2)0.1335 (2)0.0708 (6)
H17A0.40770.71770.22450.106*
H17B0.26530.68600.10910.106*
H17C0.42890.66610.07610.106*
C180.5178 (3)0.0298 (2)0.1789 (3)0.0806 (7)
H18A0.59530.02480.12400.121*
H18B0.45850.06490.16330.121*
H18C0.56990.07870.27120.121*
C190.1360 (3)0.2004 (2)0.0251 (2)0.0656 (6)
C200.0388 (3)0.1572 (3)0.0365 (3)0.0983 (9)
H20A0.08760.20900.07840.147*
H20B0.06170.17820.05100.147*
H20C0.07950.05680.08930.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0513 (9)0.0497 (9)0.1113 (12)0.0051 (7)0.0100 (8)0.0341 (9)
O20.0404 (7)0.0478 (8)0.0725 (9)0.0068 (6)0.0058 (6)0.0228 (7)
O30.0773 (12)0.1121 (15)0.0666 (11)0.0024 (10)0.0038 (9)0.0201 (10)
O40.0527 (8)0.0467 (8)0.0885 (10)0.0078 (6)0.0092 (7)0.0311 (7)
O50.0562 (9)0.0639 (10)0.0866 (10)0.0272 (7)0.0063 (7)0.0343 (8)
O60.0398 (7)0.0714 (10)0.0679 (9)0.0109 (6)0.0088 (6)0.0312 (8)
N10.0415 (9)0.0440 (9)0.0555 (9)0.0101 (7)0.0086 (7)0.0182 (7)
C10.0457 (11)0.0460 (12)0.0691 (13)0.0107 (9)0.0137 (9)0.0234 (10)
C20.0435 (10)0.0440 (11)0.0535 (11)0.0100 (8)0.0117 (8)0.0170 (9)
C30.0408 (10)0.0441 (11)0.0505 (10)0.0070 (8)0.0102 (8)0.0158 (9)
C40.0444 (10)0.0474 (11)0.0492 (10)0.0127 (9)0.0106 (8)0.0159 (9)
C50.0484 (12)0.0573 (13)0.0830 (15)0.0108 (10)0.0088 (10)0.0296 (11)
C60.0676 (15)0.0547 (14)0.1002 (17)0.0125 (11)0.0155 (13)0.0364 (13)
C70.0712 (15)0.0650 (15)0.0851 (16)0.0272 (12)0.0111 (12)0.0363 (13)
C80.0564 (12)0.0656 (15)0.0743 (14)0.0208 (11)0.0014 (10)0.0224 (12)
C90.0491 (11)0.0518 (12)0.0651 (12)0.0097 (9)0.0032 (9)0.0180 (10)
C100.0481 (11)0.0444 (11)0.0571 (11)0.0103 (9)0.0110 (9)0.0206 (9)
C110.0461 (10)0.0428 (11)0.0475 (10)0.0129 (8)0.0089 (8)0.0170 (8)
C120.0531 (12)0.0436 (11)0.0537 (11)0.0151 (9)0.0089 (9)0.0199 (9)
C130.0467 (11)0.0537 (12)0.0526 (11)0.0223 (9)0.0100 (8)0.0225 (9)
C140.0395 (10)0.0520 (12)0.0512 (11)0.0119 (9)0.0095 (8)0.0203 (9)
C150.0462 (10)0.0414 (11)0.0507 (10)0.0104 (9)0.0097 (8)0.0184 (9)
C160.0428 (10)0.0461 (11)0.0554 (11)0.0146 (8)0.0074 (8)0.0229 (9)
C170.0811 (16)0.0657 (15)0.0844 (15)0.0400 (12)0.0169 (12)0.0399 (12)
C180.0790 (16)0.0514 (14)0.119 (2)0.0195 (12)0.0154 (14)0.0435 (14)
C190.0554 (13)0.0597 (14)0.0735 (15)0.0134 (11)0.0024 (12)0.0216 (12)
C200.0475 (13)0.108 (2)0.120 (2)0.0167 (13)0.0055 (13)0.0317 (18)
Geometric parameters (Å, º) top
O1—C11.196 (2)C8—C91.375 (3)
O2—C31.383 (2)C8—H80.9300
O2—C11.392 (2)C9—H90.9300
O3—C191.195 (3)C10—C111.451 (3)
O4—C151.362 (2)C10—H100.9300
O4—C181.424 (2)C11—C121.395 (2)
O5—C131.364 (2)C11—C161.397 (2)
O5—C171.423 (2)C12—C131.384 (3)
O6—C191.350 (3)C12—H120.9300
O6—C141.392 (2)C13—C141.383 (3)
N1—C31.282 (2)C14—C151.388 (2)
N1—C21.401 (2)C15—C161.378 (2)
C1—C21.466 (3)C16—H160.9300
C2—C101.343 (3)C17—H17A0.9600
C3—C41.452 (2)C17—H17B0.9600
C4—C91.382 (3)C17—H17C0.9600
C4—C51.386 (3)C18—H18A0.9600
C5—C61.373 (3)C18—H18B0.9600
C5—H50.9300C18—H18C0.9600
C6—C71.376 (3)C19—C201.494 (3)
C6—H60.9300C20—H20A0.9600
C7—C81.368 (3)C20—H20B0.9600
C7—H70.9300C20—H20C0.9600
C3—O2—C1105.38 (14)C16—C11—C10122.31 (15)
C15—O4—C18117.16 (15)C13—C12—C11119.58 (17)
C13—O5—C17117.50 (16)C13—C12—H12120.2
C19—O6—C14117.78 (15)C11—C12—H12120.2
C3—N1—C2105.86 (15)O5—C13—C14115.29 (16)
O1—C1—O2121.92 (17)O5—C13—C12124.87 (17)
O1—C1—C2133.03 (18)C14—C13—C12119.84 (15)
O2—C1—C2105.04 (16)C13—C14—C15121.01 (16)
C10—C2—N1128.66 (17)C13—C14—O6119.01 (15)
C10—C2—C1123.40 (17)C15—C14—O6119.71 (16)
N1—C2—C1107.90 (15)O4—C15—C16124.84 (15)
N1—C3—O2115.79 (15)O4—C15—C14115.76 (16)
N1—C3—C4127.05 (17)C16—C15—C14119.40 (16)
O2—C3—C4117.16 (15)C15—C16—C11120.15 (16)
C9—C4—C5119.23 (18)C15—C16—H16119.9
C9—C4—C3121.59 (17)C11—C16—H16119.9
C5—C4—C3119.19 (17)O5—C17—H17A109.5
C6—C5—C4120.1 (2)O5—C17—H17B109.5
C6—C5—H5119.9H17A—C17—H17B109.5
C4—C5—H5119.9O5—C17—H17C109.5
C5—C6—C7120.2 (2)H17A—C17—H17C109.5
C5—C6—H6119.9H17B—C17—H17C109.5
C7—C6—H6119.9O4—C18—H18A109.5
C8—C7—C6119.8 (2)O4—C18—H18B109.5
C8—C7—H7120.1H18A—C18—H18B109.5
C6—C7—H7120.1O4—C18—H18C109.5
C7—C8—C9120.5 (2)H18A—C18—H18C109.5
C7—C8—H8119.7H18B—C18—H18C109.5
C9—C8—H8119.7O3—C19—O6122.9 (2)
C8—C9—C4120.1 (2)O3—C19—C20127.1 (2)
C8—C9—H9120.0O6—C19—C20110.0 (2)
C4—C9—H9120.0C19—C20—H20A109.5
C2—C10—C11129.06 (17)C19—C20—H20B109.5
C2—C10—H10115.5H20A—C20—H20B109.5
C11—C10—H10115.5C19—C20—H20C109.5
C12—C11—C16120.00 (16)H20A—C20—H20C109.5
C12—C11—C10117.67 (16)H20B—C20—H20C109.5
C3—O2—C1—O1178.48 (18)C2—C10—C11—C12174.82 (18)
C3—O2—C1—C20.84 (18)C2—C10—C11—C163.6 (3)
C3—N1—C2—C10179.47 (19)C16—C11—C12—C131.6 (3)
C3—N1—C2—C11.48 (19)C10—C11—C12—C13176.85 (16)
O1—C1—C2—C100.3 (4)C17—O5—C13—C14179.82 (16)
O2—C1—C2—C10179.56 (17)C17—O5—C13—C120.1 (3)
O1—C1—C2—N1177.8 (2)C11—C12—C13—O5178.12 (16)
O2—C1—C2—N11.44 (19)C11—C12—C13—C141.6 (3)
C2—N1—C3—O21.0 (2)O5—C13—C14—C15179.13 (16)
C2—N1—C3—C4179.38 (17)C12—C13—C14—C150.6 (3)
C1—O2—C3—N10.1 (2)O5—C13—C14—O65.1 (2)
C1—O2—C3—C4179.73 (15)C12—C13—C14—O6174.63 (15)
N1—C3—C4—C9178.29 (18)C19—O6—C14—C1379.7 (2)
O2—C3—C4—C92.1 (3)C19—O6—C14—C15106.2 (2)
N1—C3—C4—C51.6 (3)C18—O4—C15—C161.4 (3)
O2—C3—C4—C5178.04 (17)C18—O4—C15—C14178.39 (18)
C9—C4—C5—C60.2 (3)C13—C14—C15—O4179.81 (16)
C3—C4—C5—C6179.96 (19)O6—C14—C15—O46.2 (2)
C4—C5—C6—C70.1 (3)C13—C14—C15—C160.4 (3)
C5—C6—C7—C80.3 (4)O6—C14—C15—C16173.58 (15)
C6—C7—C8—C90.2 (3)O4—C15—C16—C11179.81 (16)
C7—C8—C9—C40.1 (3)C14—C15—C16—C110.4 (3)
C5—C4—C9—C80.3 (3)C12—C11—C16—C150.6 (3)
C3—C4—C9—C8179.89 (18)C10—C11—C16—C15177.78 (17)
N1—C2—C10—C111.5 (3)C14—O6—C19—O39.4 (3)
C1—C2—C10—C11176.21 (17)C14—O6—C19—C20170.48 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O1i0.932.563.483 (2)172
Symmetry code: (i) x+3, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC20H17NO6
Mr367.35
Crystal system, space groupTriclinic, P1
Temperature (K)273
a, b, c (Å)8.8400 (13), 10.4431 (15), 10.9693 (16)
α, β, γ (°)111.074 (6), 96.544 (6), 102.119 (6)
V3)903.7 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.15 × 0.12 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.985, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections
10391, 3176, 2244
Rint0.028
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.117, 1.02
No. of reflections3176
No. of parameters248
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.16

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O1i0.932.563.483 (2)172
Symmetry code: (i) x+3, y+1, z+1.
 

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