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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o217.
Published online 2007 December 6. doi:  10.1107/S1600536807060588
PMCID: PMC2915278

3-[(Hydr­oxy)(4-isoprop­oxy-2-methoxy­phen­yl)methyl­ene]-1-isopropyl­pyrrol­idine-2,4-dione

Abstract

The title compound, C18H23NO5, a potential herbicide, has an enol group that is intra­molecularly hydrogen bonded to a keto O atom. The dihedral angle between the six-membered ring formed by the enol group and the aromatic benzene ring is 53.35 (6)°.

Related literature

For structural and herbicidal literature on this class of compounds, see: Ellis & Spek (2001 [triangle]); Holzapfel et al. (1970 [triangle]); Rinehart et al. (1971 [triangle], 1963 [triangle]); Matsuo et al. (1980 [triangle]); van Rooyen (1992 [triangle]); Stickings (1959 [triangle]); Van Der Baan et al. (1978 [triangle]); Xu (2005 [triangle]); Zhu, Hu & Yang (2004 [triangle]); Zhu, Song, Li et al. (2004 [triangle]); Zhu, Song, Yao et al. (2004 [triangle]). For standard bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o217-scheme1.jpg

Experimental

Crystal data

  • C18H23NO5
  • M r = 333.37
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o217-efi1.jpg
  • a = 14.694 (2) Å
  • b = 12.249 (2) Å
  • c = 20.308 (3) Å
  • β = 103.864 (3)°
  • V = 3548.5 (10) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 294 (2) K
  • 0.26 × 0.24 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 9820 measured reflections
  • 3622 independent reflections
  • 2199 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.131
  • S = 1.04
  • 3622 reflections
  • 223 parameters
  • 12 restraints
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1999 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1999 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807060588/ng2379sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807060588/ng2379Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (grant No. 20772066).

supplementary crystallographic information

Comment

Many compounds containing the 3-acylpyrrolidine-2,4-dione system belong to heterocycles with antibiotic activity, suchas tenuazonic acid (Stickings, 1959), streptolydigin (Rinehart et al., 1963), tirandamycin (Rinehart et al., 1971), malonomycin (Van Der Baan et al., 1978), alpha-cyclopiazonic acid (Stickings, 1959; van Rooyen, 1992) and bata-cyclopiazonic acid (Holzapfel et al., 1970). All these compounds possess a 3-acyltetramic acid grouping as a tricarbonylmethane fragment. Most of the excellent inhibitors of p-hydroxyphenylpyruvate dioxygenase also possess similar characteristics, which are crucial for their two kinds of bioactivity (Zhu, Hu & Yang, 2004). In order to develop new herbicides, we synthesized the title compound. The molecular structure of the title compound is shown in Fig. 1. Atom H3, involved in intramolecular hydrogen bonding between atoms O3 and O4, was assigned to O3 rather than to O4. The C13?O4 distance is 1.251 (2) Å, which is longer than the normal carbonyl bond length (C13?O1) of 1.219 (2) Å. In contrast, the C11?O3 distance [1.318 (2) Å] is intermediate between a normal carbonyl C?O double bond and a C—O single-bond length (Allen et al., 1987) (Table 1). A similar situation was reported for 3-(1-hydroxyethylidene)-1-phenylpyrrolidine-2,4-dione (Ellis & Spek, 2001), 1-benzyl-3-(alpha-hydroxybenzylidene)pyrrolidine-2,4-dione, (I) (Zhu, Song, Li et al., 2004), 1-tert-butyl-3-(alpha-hydroxy-4-isopropylbenzylidene)pyrrolidine-2,4-dione, (II) (Xu, 2005), and 3-(alpha-hydroxyl-2-methoxylbenzylidene)-1-isopropylpyrrolidine-2,4-dione, (III) (Zhu, Song, Yao et al., 2004). The dihedral angle formed by the enol ring A with the benzene ring is 53.35 (6)°, which is larger than the dihedral angles for (I), (II) (10 and 21°, respectively) and smaller than the dihedral angle for (III) (53°). The crystal structure of the title compound also involves a weak intramolecular C—H···O hydrogenbonding interactions (Table 2).

Experimental

The title compound was obtained according to the procedure reported by Matsuo et al. (1980). Colourless single crystals of the title compound were obtained by recrystallization of 1-isopropyl-3-(α<i/>-hydroxy-4-isopropoxyl-2-methoxybenzylidene) pyrrolidine-2,4-dione from petroleum ether and ethyl acetate(1:3).

Refinement

All H atoms were placed in calculated positions, with C—H = 0.93 or 0.96 Å and O—H = 0.82 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). Friedel pairs were not merged.

Figures

Fig. 1.
View of the title compound, with displacement ellipsoids drawn at the 30% probability level.

Crystal data

C18H23NO5Z = 8
Mr = 333.37F000 = 1424
Monoclinic, C2/cDx = 1.248 Mg m3
Hall symbol: -C 2ycMo Kα radiation λ = 0.71073 Å
a = 14.694 (2) Åθ = 2.6–23.1º
b = 12.249 (2) ŵ = 0.09 mm1
c = 20.308 (3) ÅT = 294 (2) K
β = 103.864 (3)ºPrism, colourless
V = 3548.5 (10) Å30.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer2199 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Monochromator: graphiteθmax = 26.4º
T = 294(2) Kθmin = 2.1º
[var phi] and ω scansh = −18→8
Absorption correction: nonek = −15→15
9820 measured reflectionsl = −24→25
3622 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.131  w = 1/[σ2(Fo2) + (0.066P)2 + 0.41P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3622 reflectionsΔρmax = 0.19 e Å3
223 parametersΔρmin = −0.20 e Å3
12 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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 (Å2)

xyzUiso*/Ueq
O10.08411 (12)0.33480 (12)0.57101 (7)0.0604 (4)
O20.17331 (10)0.25752 (11)0.36755 (7)0.0532 (4)
O30.10441 (13)0.05253 (13)0.31692 (7)0.0695 (5)
H30.11640.00470.29210.104*
O40.18049 (11)−0.11472 (12)0.27727 (7)0.0566 (4)
O50.28614 (11)−0.06071 (13)0.51329 (7)0.0625 (5)
N10.28941 (12)−0.19911 (14)0.36200 (8)0.0452 (4)
C1−0.0325 (2)0.2778 (3)0.63023 (14)0.0851 (9)
H1A−0.07070.33960.61240.128*
H1B−0.04170.25970.67420.128*
H1C−0.04990.21670.60030.128*
C20.06866 (16)0.30512 (19)0.63625 (11)0.0552 (6)
H20.10760.24190.65420.066*
C30.1002 (2)0.4022 (2)0.68087 (13)0.0837 (9)
H3A0.16480.41720.68260.126*
H3B0.09310.38710.72580.126*
H3C0.06280.46450.66280.126*
C40.09829 (14)0.25628 (16)0.52731 (10)0.0441 (5)
C50.12539 (13)0.29580 (16)0.47092 (10)0.0427 (5)
H50.13140.37060.46550.051*
C60.14353 (13)0.22495 (16)0.42277 (9)0.0400 (5)
C70.13459 (14)0.11166 (15)0.43064 (10)0.0416 (5)
C80.10772 (15)0.07488 (17)0.48725 (11)0.0509 (5)
H80.10230.00010.49310.061*
C90.08852 (16)0.14464 (17)0.53562 (11)0.0531 (6)
H90.06950.11750.57290.064*
C100.18157 (18)0.37182 (18)0.35704 (11)0.0608 (6)
H10A0.12050.40480.34770.091*
H10B0.20910.38350.31930.091*
H10C0.22060.40410.39700.091*
C110.15126 (14)0.03387 (16)0.37983 (10)0.0442 (5)
C120.20977 (14)−0.05513 (15)0.39318 (9)0.0391 (5)
C130.22342 (14)−0.12462 (15)0.33812 (10)0.0409 (5)
C140.32846 (17)−0.18606 (18)0.43457 (10)0.0555 (6)
H14A0.3948−0.16920.44390.067*
H14B0.3199−0.25200.45890.067*
C150.27400 (14)−0.09173 (16)0.45477 (10)0.0449 (5)
C160.32451 (15)−0.27819 (16)0.31986 (10)0.0477 (5)
H160.2810−0.27830.27500.057*
C170.41877 (18)−0.2440 (2)0.31078 (13)0.0768 (8)
H17A0.4149−0.17110.29300.115*
H17B0.4381−0.29300.27980.115*
H17C0.4636−0.24610.35380.115*
C180.3244 (3)−0.3906 (2)0.34875 (15)0.1083 (12)
H18A0.3691−0.39420.39170.162*
H18B0.3408−0.44270.31820.162*
H18C0.2630−0.40710.35480.162*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0880 (12)0.0482 (9)0.0541 (9)0.0052 (8)0.0351 (8)−0.0034 (7)
O20.0704 (10)0.0466 (9)0.0480 (8)−0.0046 (7)0.0246 (8)−0.0024 (7)
O30.0945 (13)0.0603 (11)0.0440 (9)0.0274 (9)−0.0025 (9)−0.0056 (7)
O40.0720 (11)0.0573 (10)0.0373 (8)0.0081 (8)0.0068 (7)−0.0042 (7)
O50.0824 (12)0.0634 (10)0.0395 (9)0.0174 (8)0.0101 (8)−0.0075 (7)
N10.0523 (10)0.0456 (10)0.0383 (9)0.0075 (8)0.0118 (8)−0.0051 (7)
C10.0769 (19)0.102 (2)0.0840 (19)−0.0169 (16)0.0350 (15)−0.0154 (17)
C20.0629 (15)0.0592 (14)0.0482 (13)−0.0004 (11)0.0226 (11)−0.0032 (11)
C30.104 (2)0.087 (2)0.0674 (17)−0.0210 (17)0.0350 (16)−0.0227 (15)
C40.0459 (12)0.0423 (12)0.0453 (11)0.0049 (9)0.0131 (9)−0.0042 (10)
C50.0466 (12)0.0352 (11)0.0465 (12)0.0000 (9)0.0120 (9)−0.0009 (9)
C60.0353 (10)0.0439 (11)0.0399 (11)0.0016 (9)0.0072 (8)−0.0001 (9)
C70.0433 (11)0.0403 (11)0.0399 (11)0.0061 (9)0.0071 (9)−0.0007 (9)
C80.0634 (14)0.0361 (11)0.0548 (13)0.0048 (10)0.0175 (11)0.0019 (10)
C90.0662 (15)0.0485 (13)0.0504 (13)0.0024 (11)0.0254 (11)0.0041 (10)
C100.0796 (17)0.0506 (14)0.0574 (14)−0.0129 (12)0.0266 (13)0.0002 (11)
C110.0503 (12)0.0426 (12)0.0384 (11)0.0009 (10)0.0082 (9)0.0016 (9)
C120.0456 (11)0.0357 (10)0.0373 (11)−0.0017 (9)0.0123 (9)−0.0014 (8)
C130.0449 (12)0.0377 (11)0.0413 (12)−0.0047 (9)0.0129 (9)−0.0008 (9)
C140.0636 (15)0.0585 (14)0.0424 (12)0.0162 (11)0.0087 (10)−0.0029 (10)
C150.0532 (13)0.0428 (11)0.0401 (12)0.0016 (9)0.0137 (10)−0.0014 (9)
C160.0599 (14)0.0442 (12)0.0418 (11)0.0064 (10)0.0178 (10)−0.0059 (9)
C170.0618 (16)0.100 (2)0.0716 (16)0.0071 (14)0.0221 (13)−0.0198 (14)
C180.200 (3)0.0501 (16)0.099 (2)0.0141 (18)0.084 (2)−0.0003 (14)

Geometric parameters (Å, °)

O1—C41.358 (2)C6—C71.407 (3)
O1—C21.443 (3)C7—C81.378 (3)
O2—C61.358 (2)C7—C111.468 (3)
O2—C101.426 (2)C8—C91.381 (3)
O3—C111.318 (2)C8—H80.9300
O3—H30.8200C9—H90.9300
O4—C131.251 (2)C10—H10A0.9600
O5—C151.219 (2)C10—H10B0.9600
N1—C131.335 (3)C10—H10C0.9600
N1—C141.457 (3)C11—C121.375 (3)
N1—C161.466 (2)C12—C151.446 (3)
C1—C21.500 (4)C12—C131.457 (3)
C1—H1A0.9600C14—C151.517 (3)
C1—H1B0.9600C14—H14A0.9700
C1—H1C0.9600C14—H14B0.9700
C2—C31.500 (3)C16—C181.497 (3)
C2—H20.9800C16—C171.500 (3)
C3—H3A0.9600C16—H160.9800
C3—H3B0.9600C17—H17A0.9600
C3—H3C0.9600C17—H17B0.9600
C4—C51.387 (3)C17—H17C0.9600
C4—C91.389 (3)C18—H18A0.9600
C5—C61.380 (3)C18—H18B0.9600
C5—H50.9300C18—H18C0.9600
C4—O1—C2120.27 (16)O2—C10—H10A109.5
C6—O2—C10117.91 (15)O2—C10—H10B109.5
C11—O3—H3109.5H10A—C10—H10B109.5
C13—N1—C14111.61 (16)O2—C10—H10C109.5
C13—N1—C16124.48 (16)H10A—C10—H10C109.5
C14—N1—C16123.71 (16)H10B—C10—H10C109.5
C2—C1—H1A109.5O3—C11—C12119.05 (17)
C2—C1—H1B109.5O3—C11—C7115.64 (17)
H1A—C1—H1B109.5C12—C11—C7125.31 (18)
C2—C1—H1C109.5C11—C12—C15131.63 (18)
H1A—C1—H1C109.5C11—C12—C13120.43 (17)
H1B—C1—H1C109.5C15—C12—C13107.55 (17)
O1—C2—C3105.14 (19)O4—C13—N1125.12 (18)
O1—C2—C1110.6 (2)O4—C13—C12124.87 (18)
C3—C2—C1112.5 (2)N1—C13—C12110.00 (17)
O1—C2—H2109.5N1—C14—C15104.58 (16)
C3—C2—H2109.5N1—C14—H14A110.8
C1—C2—H2109.5C15—C14—H14A110.8
C2—C3—H3A109.5N1—C14—H14B110.8
C2—C3—H3B109.5C15—C14—H14B110.8
H3A—C3—H3B109.5H14A—C14—H14B108.9
C2—C3—H3C109.5O5—C15—C12131.24 (19)
H3A—C3—H3C109.5O5—C15—C14122.51 (18)
H3B—C3—H3C109.5C12—C15—C14106.23 (16)
O1—C4—C5114.32 (18)N1—C16—C18110.20 (17)
O1—C4—C9125.52 (19)N1—C16—C17110.60 (18)
C5—C4—C9120.15 (18)C18—C16—C17113.1 (2)
C6—C5—C4120.53 (18)N1—C16—H16107.6
C6—C5—H5119.7C18—C16—H16107.6
C4—C5—H5119.7C17—C16—H16107.6
O2—C6—C5123.75 (18)C16—C17—H17A109.5
O2—C6—C7116.18 (17)C16—C17—H17B109.5
C5—C6—C7120.04 (18)H17A—C17—H17B109.5
C8—C7—C6118.08 (18)C16—C17—H17C109.5
C8—C7—C11120.26 (18)H17A—C17—H17C109.5
C6—C7—C11121.64 (18)H17B—C17—H17C109.5
C7—C8—C9122.64 (19)C16—C18—H18A109.5
C7—C8—H8118.7C16—C18—H18B109.5
C9—C8—H8118.7H18A—C18—H18B109.5
C8—C9—C4118.54 (19)C16—C18—H18C109.5
C8—C9—H9120.7H18A—C18—H18C109.5
C4—C9—H9120.7H18B—C18—H18C109.5
C4—O1—C2—C3154.3 (2)C7—C11—C12—C15−5.9 (4)
C4—O1—C2—C1−84.0 (2)O3—C11—C12—C133.1 (3)
C2—O1—C4—C5−171.26 (18)C7—C11—C12—C13−177.76 (17)
C2—O1—C4—C98.2 (3)C14—N1—C13—O4177.57 (19)
O1—C4—C5—C6179.05 (17)C16—N1—C13—O42.7 (3)
C9—C4—C5—C6−0.4 (3)C14—N1—C13—C12−1.4 (2)
C10—O2—C6—C5−3.4 (3)C16—N1—C13—C12−176.37 (17)
C10—O2—C6—C7178.82 (18)C11—C12—C13—O4−4.9 (3)
C4—C5—C6—O2−177.72 (17)C15—C12—C13—O4−178.60 (18)
C4—C5—C6—C70.0 (3)C11—C12—C13—N1174.08 (18)
O2—C6—C7—C8177.77 (18)C15—C12—C13—N10.4 (2)
C5—C6—C7—C8−0.1 (3)C13—N1—C14—C151.8 (2)
O2—C6—C7—C11−3.5 (3)C16—N1—C14—C15176.78 (18)
C5—C6—C7—C11178.64 (18)C11—C12—C15—O59.5 (4)
C6—C7—C8—C90.7 (3)C13—C12—C15—O5−177.8 (2)
C11—C7—C8—C9−178.1 (2)C11—C12—C15—C14−172.0 (2)
C7—C8—C9—C4−1.1 (3)C13—C12—C15—C140.7 (2)
O1—C4—C9—C8−178.5 (2)N1—C14—C15—O5177.22 (19)
C5—C4—C9—C81.0 (3)N1—C14—C15—C12−1.5 (2)
C8—C7—C11—O3126.2 (2)C13—N1—C16—C18−130.9 (3)
C6—C7—C11—O3−52.5 (3)C14—N1—C16—C1854.8 (3)
C8—C7—C11—C12−53.0 (3)C13—N1—C16—C17103.3 (2)
C6—C7—C11—C12128.3 (2)C14—N1—C16—C17−71.0 (3)
O3—C11—C12—C15175.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O40.821.802.555 (2)152
C16—H16···O40.982.502.891 (2)104

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2379).

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