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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o855.
Published online 2008 April 16. doi:  10.1107/S1600536808009823
PMCID: PMC2961278

1-(4-Isopropyl­phen­yl)-5-(4-methoxy­phen­yl)pyrazolidin-3-one

Abstract

In the mol­ecule of the title compound, C19H22N2O2, the pyrazolidinone ring has an envelope conformation, with the C atom attached to the 4-methoxy­phenyl ring displaced by 0.354 (3) Å from the plane of the other ring atoms. The 4-iso­propyl­phenyl ring is oriented with respect to the 4-meth­oxy­phenyl ring at a dihedral angle of 88.94 (3)°. Intra­molecular C—H(...)N hydrogen bonds result in the formation of two planar five-membered rings, which are oriented with respect to the adjacent 4-isopropyl­phenyl and 4-meth­oxy­phenyl rings at dihedral angles of 4.05 (3) and 0.50 (3)°, respectively. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds link the mol­ecules into centrosymmetric dimers.

Related literature

For general background, see: Menozzi et al. (1990 [triangle]); Brooks et al. (1990 [triangle]); Greenwood et al. (1995 [triangle]).

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Object name is e-64-0o855-scheme1.jpg

Experimental

Crystal data

  • C19H22N2O2
  • M r = 310.39
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o855-efi1.jpg
  • a = 14.737 (3) Å
  • b = 7.1490 (14) Å
  • c = 17.493 (4) Å
  • β = 112.03 (3)°
  • V = 1708.4 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 294 (2) K
  • 0.40 × 0.30 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.969, T max = 0.984
  • 3472 measured reflections
  • 3340 independent reflections
  • 1835 reflections with I > 2σ(I)
  • R int = 0.052
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.078
  • wR(F 2) = 0.163
  • S = 1.06
  • 3340 reflections
  • 202 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.78 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and PLATON (Spek, 2003 [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/S1600536808009823/hk2451sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009823/hk2451Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

Pyrazolidin-3-one derivatives are important chemical materials of effective medicines used for treatment of inflammation. They are of great interest because of their biological properties, such as antipyretic activity (Menozzi et al., 1990), liphoxygenase enzyme inhibition (Brooks et al., 1990) and cholecystokinin (CCK) receptor antagonist activity (Greenwood et al., 1995). We report herein the crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1), rings A (C4-C9) and C (C13-C18) are, of course, planar. The dihedral angle between them is A/C = 88.94 (3)°. Ring B (N1/N2/C10-C12) has envelope conformation with atom C10 displaced by 0.354 (3) Å from the plane of the other ring atoms. The intramolecular C-H···N hydrogen bonds (Table 1) result in the formation of two planar five-membered rings D (N1/N2/C7/C8/H8A) and E (N1/C10/C13/C14/H14A). They are oriented with respect to the adjacent rings at dihedral angles of A/D = 4.05 (3)° and C/E = 0.50 (3)°. So, they are also nearly coplanar.

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, ethanolamine (4 ml) and n-butanol (20 ml) were added to a solution of sodium (40 mmol) in anhydrous methanol (9 mol). Then, the methanol was removed by distillation and 3-(4-methylphenyl) acrylate was added. The mixture was refluxed for 1 h at the temperature above 373 K, after which isopropyphenyl hydrazine (4 ml) was added. The reactants were refluxed for a further 10 h, left to cool to room temperature, and then acidified with acetic acid (36%), allowed to stand, filtered, and the filter cake was crystallized from ethyl acetate to give the title compound (m.p. 435-437 K). It was crystallized by the slow evaporation of an ethyl acetate solution.

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93, 0.98, 0.97 and 0.96 Å for aromatic, methine, methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bond is shown as dashed line.
Fig. 2.
A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C19H22N2O2F000 = 664
Mr = 310.39Dx = 1.207 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 14.737 (3) Åθ = 9–13º
b = 7.1490 (14) ŵ = 0.08 mm1
c = 17.493 (4) ÅT = 294 (2) K
β = 112.03 (3)ºBlock, colorless
V = 1708.4 (7) Å30.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.052
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 1.6º
T = 294(2) Kh = −18→16
ω/2θ scansk = 0→8
Absorption correction: ψ scan(North et al., 1968)l = 0→21
Tmin = 0.969, Tmax = 0.9843 standard reflections
3472 measured reflections every 120 min
3340 independent reflections intensity decay: none
1835 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.078H-atom parameters constrained
wR(F2) = 0.163  w = 1/[σ2(Fo2) + (0.008P)2 + 3.2P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3340 reflectionsΔρmax = 0.38 e Å3
202 parametersΔρmin = −0.78 e Å3
1 restraintExtinction 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 > 2sigma(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
O10.52570 (18)0.7545 (4)1.04046 (16)0.0569 (7)
N10.2835 (2)0.9106 (4)0.97974 (18)0.0486 (8)
N20.3849 (2)0.9266 (4)0.99532 (18)0.0508 (8)
H2A0.41041.02780.98590.061*
C10.0956 (5)1.2768 (9)1.2266 (4)0.117 (2)
H1A0.07721.36081.26110.176*
H1B0.13831.18211.26010.176*
H1C0.03801.21911.18760.176*
O20.0840 (2)0.3384 (4)0.67816 (16)0.0656 (8)
C20.0897 (4)1.5470 (7)1.1350 (3)0.091
H2B0.07051.62381.17140.136*
H2C0.03231.50351.09060.136*
H2D0.12941.61891.11310.136*
C30.1471 (4)1.3827 (7)1.1817 (3)0.0881 (16)
H3A0.20571.43521.22440.106*
C40.1840 (3)1.2577 (6)1.1290 (3)0.0657 (11)
C50.1216 (3)1.1481 (7)1.0656 (3)0.0792 (14)
H5A0.05491.15071.05480.095*
C60.1557 (3)1.0349 (6)1.0180 (3)0.0684 (12)
H6A0.11160.96490.97540.082*
C70.2539 (3)1.0251 (5)1.0332 (2)0.0467 (9)
C80.3165 (3)1.1359 (5)1.0951 (2)0.0538 (10)
H8A0.38311.13481.10530.065*
C90.2817 (3)1.2487 (6)1.1424 (3)0.0626 (11)
H9A0.32571.32031.18430.075*
C100.2671 (3)0.7054 (5)0.9853 (2)0.0485 (9)
H10A0.22510.68781.01690.058*
C110.3691 (3)0.6265 (5)1.0361 (2)0.0522 (10)
H11A0.37800.61231.09360.063*
H11B0.37920.50641.01470.063*
C120.4378 (3)0.7731 (5)1.0257 (2)0.0473 (9)
C130.2185 (3)0.6143 (5)0.9026 (2)0.0489 (9)
C140.1919 (3)0.7046 (6)0.8282 (2)0.0556 (10)
H14A0.20440.83200.82740.067*
C150.1471 (3)0.6114 (6)0.7545 (2)0.0583 (11)
H15A0.12890.67680.70500.070*
C160.1289 (3)0.4205 (6)0.7537 (2)0.0544 (10)
C170.1560 (3)0.3291 (6)0.8282 (2)0.0691 (12)
H17A0.14390.20170.82920.083*
C180.2002 (3)0.4224 (5)0.9003 (2)0.0636 (12)
H18A0.21880.35650.94970.076*
C190.0726 (3)0.1427 (6)0.6765 (3)0.0721 (13)
H19A0.03990.10190.62060.108*
H19B0.03440.10840.70830.108*
H19C0.13580.08450.69960.108*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0495 (16)0.0490 (16)0.0681 (17)0.0004 (13)0.0174 (13)0.0023 (13)
N10.0495 (18)0.0428 (17)0.0569 (19)−0.0016 (15)0.0238 (15)0.0036 (15)
N20.0493 (18)0.0411 (17)0.068 (2)−0.0024 (15)0.0287 (16)0.0015 (16)
C10.158 (6)0.112 (5)0.131 (5)0.002 (4)0.110 (5)−0.012 (4)
O20.0709 (19)0.0627 (19)0.0500 (16)−0.0031 (15)0.0077 (14)−0.0046 (14)
C20.0910.0910.0910.0000.0340.000
C30.098 (4)0.083 (4)0.105 (4)0.008 (3)0.064 (3)−0.003 (3)
C40.071 (3)0.059 (3)0.078 (3)−0.003 (2)0.042 (2)−0.006 (2)
C50.051 (2)0.092 (4)0.105 (4)0.001 (3)0.040 (3)−0.009 (3)
C60.054 (2)0.068 (3)0.089 (3)−0.016 (2)0.034 (2)−0.020 (3)
C70.047 (2)0.042 (2)0.053 (2)−0.0051 (17)0.0211 (18)−0.0005 (18)
C80.051 (2)0.055 (2)0.055 (2)−0.0008 (19)0.0204 (19)0.011 (2)
C90.074 (3)0.057 (3)0.061 (3)−0.007 (2)0.029 (2)−0.008 (2)
C100.051 (2)0.044 (2)0.055 (2)−0.0040 (18)0.0254 (18)−0.0009 (18)
C110.063 (2)0.041 (2)0.046 (2)−0.0069 (19)0.0129 (18)−0.0012 (17)
C120.056 (2)0.044 (2)0.042 (2)−0.0043 (19)0.0191 (17)−0.0029 (17)
C130.047 (2)0.045 (2)0.050 (2)−0.0016 (18)0.0125 (17)0.0050 (18)
C140.057 (2)0.045 (2)0.058 (2)−0.0012 (19)0.014 (2)0.0083 (19)
C150.065 (3)0.056 (3)0.046 (2)0.001 (2)0.0116 (19)0.008 (2)
C160.045 (2)0.061 (3)0.049 (2)−0.0008 (19)0.0084 (17)0.000 (2)
C170.089 (3)0.046 (2)0.057 (3)−0.012 (2)0.010 (2)0.001 (2)
C180.090 (3)0.042 (2)0.049 (2)−0.008 (2)0.014 (2)0.0026 (19)
C190.075 (3)0.069 (3)0.067 (3)−0.017 (3)0.020 (2)−0.017 (2)

Geometric parameters (Å, °)

O1—C121.229 (4)C7—C81.379 (5)
N1—N21.418 (4)C8—C91.383 (5)
N1—C71.429 (4)C8—H8A0.9300
N1—C101.496 (4)C9—H9A0.9300
N2—C121.336 (4)C10—C131.501 (5)
N2—H2A0.8600C10—C111.538 (5)
C1—C31.488 (6)C10—H10A0.9800
C1—H1A0.9600C11—C121.515 (5)
C1—H1B0.9600C11—H11A0.9700
C1—H1C0.9600C11—H11B0.9700
O2—C161.368 (4)C13—C141.372 (5)
O2—C191.407 (5)C13—C181.396 (5)
C2—C31.498 (6)C14—C151.380 (5)
C2—H2B0.9600C14—H14A0.9300
C2—H2C0.9600C15—C161.390 (5)
C2—H2D0.9600C15—H15A0.9300
C3—C41.524 (6)C16—C171.378 (5)
C3—H3A0.9800C17—C181.358 (5)
C4—C91.370 (5)C17—H17A0.9300
C4—C51.386 (6)C18—H18A0.9300
C5—C61.384 (6)C19—H19A0.9600
C5—H5A0.9300C19—H19B0.9600
C6—C71.372 (5)C19—H19C0.9600
C6—H6A0.9300
N2—N1—C7112.7 (3)C4—C9—H9A119.1
N2—N1—C10104.5 (3)C8—C9—H9A119.1
C7—N1—C10115.0 (3)N1—C10—C13113.1 (3)
C12—N2—N1115.2 (3)N1—C10—C11104.5 (3)
C12—N2—H2A122.4C13—C10—C11114.0 (3)
N1—N2—H2A122.4N1—C10—H10A108.3
C3—C1—H1A109.5C13—C10—H10A108.3
C3—C1—H1B109.5C11—C10—H10A108.3
H1A—C1—H1B109.5C12—C11—C10103.3 (3)
C3—C1—H1C109.5C12—C11—H11A111.1
H1A—C1—H1C109.5C10—C11—H11A111.1
H1B—C1—H1C109.5C12—C11—H11B111.1
C16—O2—C19117.2 (3)C10—C11—H11B111.1
C3—C2—H2B109.5H11A—C11—H11B109.1
C3—C2—H2C109.5O1—C12—N2125.8 (3)
H2B—C2—H2C109.5O1—C12—C11126.8 (3)
C3—C2—H2D109.5N2—C12—C11107.4 (3)
H2B—C2—H2D109.5C14—C13—C18116.9 (4)
H2C—C2—H2D109.5C14—C13—C10125.0 (3)
C1—C3—C2113.1 (4)C18—C13—C10118.1 (3)
C1—C3—C4112.9 (4)C13—C14—C15121.7 (4)
C2—C3—C4112.7 (4)C13—C14—H14A119.1
C1—C3—H3A105.8C15—C14—H14A119.1
C2—C3—H3A105.8C14—C15—C16120.4 (4)
C4—C3—H3A105.8C14—C15—H15A119.8
C9—C4—C5116.7 (4)C16—C15—H15A119.8
C9—C4—C3121.0 (4)O2—C16—C17125.1 (4)
C5—C4—C3122.4 (4)O2—C16—C15116.9 (4)
C6—C5—C4122.0 (4)C17—C16—C15118.0 (4)
C6—C5—H5A119.0C18—C17—C16121.0 (4)
C4—C5—H5A119.0C18—C17—H17A119.5
C7—C6—C5120.5 (4)C16—C17—H17A119.5
C7—C6—H6A119.8C17—C18—C13122.0 (4)
C5—C6—H6A119.8C17—C18—H18A119.0
C6—C7—C8118.0 (4)C13—C18—H18A119.0
C6—C7—N1117.5 (3)O2—C19—H19A109.5
C8—C7—N1124.4 (3)O2—C19—H19B109.5
C7—C8—C9121.0 (4)H19A—C19—H19B109.5
C7—C8—H8A119.5O2—C19—H19C109.5
C9—C8—H8A119.5H19A—C19—H19C109.5
C4—C9—C8121.7 (4)H19B—C19—H19C109.5
C7—N1—N2—C12112.7 (3)C7—N1—C10—C11−103.1 (3)
C10—N1—N2—C12−12.9 (4)N1—C10—C11—C12−21.7 (4)
C1—C3—C4—C9−120.1 (5)C13—C10—C11—C12102.3 (3)
C2—C3—C4—C9110.2 (5)N1—N2—C12—O1176.9 (3)
C1—C3—C4—C559.8 (7)N1—N2—C12—C11−1.5 (4)
C2—C3—C4—C5−69.8 (6)C10—C11—C12—O1−163.7 (4)
C9—C4—C5—C60.0 (7)C10—C11—C12—N214.7 (4)
C3—C4—C5—C6−180.0 (4)N1—C10—C13—C140.7 (5)
C4—C5—C6—C71.2 (8)C11—C10—C13—C14−118.5 (4)
C5—C6—C7—C8−2.2 (6)N1—C10—C13—C18179.5 (4)
C5—C6—C7—N1−177.8 (4)C11—C10—C13—C1860.3 (5)
N2—N1—C7—C6173.6 (3)C18—C13—C14—C151.4 (6)
C10—N1—C7—C6−66.8 (5)C10—C13—C14—C15−179.8 (4)
N2—N1—C7—C8−1.8 (5)C13—C14—C15—C16−1.0 (6)
C10—N1—C7—C8117.9 (4)C19—O2—C16—C17−5.9 (6)
C6—C7—C8—C92.1 (6)C19—O2—C16—C15174.9 (4)
N1—C7—C8—C9177.4 (4)C14—C15—C16—O2179.8 (3)
C5—C4—C9—C80.0 (7)C14—C15—C16—C170.6 (6)
C3—C4—C9—C8179.9 (4)O2—C16—C17—C18−179.9 (4)
C7—C8—C9—C4−1.1 (6)C15—C16—C17—C18−0.7 (7)
N2—N1—C10—C13−103.6 (3)C16—C17—C18—C131.2 (7)
C7—N1—C10—C13132.3 (3)C14—C13—C18—C17−1.5 (7)
N2—N1—C10—C1121.0 (4)C10—C13—C18—C17179.6 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.861.962.819 (4)175
C8—H8A···N20.932.442.761 (5)100
C14—H14A···N10.932.542.887 (5)102

Symmetry codes: (i) −x+1, −y+2, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2451).

References

  • Brooks, D. W., Basha, A., Gunn, B. P. & Bhatia, P. A. (1990). US Patent No. 4 970 210.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Greenwood, B., Helton, D. R. & Howbert, J. J. (1995). US Patent No. 5 399 565.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Menozzi, G., Mosti, L. & Schenone, P. (1990). Il Farmaco, 45, 167–186. [PubMed]
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography