5 (4 Meth­oxy­phen­yl) 1 phenyl­pyrazolidin 3 one

organic papers

o2246

16H16N2O2 doi:10.1107/S1600536805019227 Acta Cryst.(2005). E61, o2246–o2247

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

5-(4-Methoxyphenyl)-1-phenylpyrazolidin-3-one

Hong Shi, Hong-Jun Zhu, Peng-Wei Yin, Jin-Tang Wang and Xiao-Lan Shi*

Department of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People’s Republic of China

Correspondence e-mail: zhuhj@njut.edu.cn

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C–C) = 0.003 A˚ Rfactor = 0.048 wRfactor = 0.162

Data-to-parameter ratio = 14.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, C16H16N2O2, was synthesized by the

reaction of ethyl 3-(4-methylphenyl)acrylate and phenyl-hydrazine. There are intermolecular N—H O hydrogen bonds and C—H interactions.

Comment

Pyrazolidin-3-one derivatives are effective medicines used in the treatment of inflammation and related disorders (Reddy & Bell, 2003), as liphoxygenase enzyme inhibitors (Brookset al., 1990), and in pesticides and herbicides (Tanaka et al., 1999). We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. The pyrazolidine ring (N1/N2/C10/C9/C8) adopts a twisted conformation (Lowet al., 2003). The dihedral angle between the C8/C9/C10 and C8/N1/N2/C10 planes is 15.69 (19)_{. In the} crystal structure, molecules are linked by N—H O hydrogen bonds and C—H interactions (Table 2), forming a

three-Received 12 May 2005 Accepted 16 June 2005 Online 24 June 2005

Figure 1

dimensional network (Fig. 2). The phenyl ring acts as a double C—H hydrogen-bond acceptor, accepting one H

bond from C6 of a methoxyphenyl group on one side and another H bond from C15 of a phenyl group on the other side. The dihedral angle between the two aromatic rings within the molecule is 79.5 (1)_{. Owing to the presence of the} carbonyl group in the pyrazolidine ring, the acidity of the H atom on C9 may be increased (Zhuet al., 2004).

Experimental

To a solution of sodium (40 mmol) in anhydrous methanol (9 mol) were added ethanolamine (4 ml) and n-butanol (20 ml). The methanol was then removed by distillation and 3-(4-methylphenyl)-acrylic acid was added. The mixture was refluxed for 1 h at a temperature above 373 K, after which phenylhydrazine (4 ml) was added. The reactants were refluxed for a further 7 h, left to cool to room temperature, acidified with 36% acetic acid and then allowed to stand. After filtration, the filter cake was crystallized from ethyl acetate to give pure compound (I) (m.p. 435–437 K). The compound was crystallized twice by slow evaporation of an ethyl acetate solution and crystals suitable for X-ray diffraction analysis were obtained.

Crystal data

C16H16N2O2 Mr= 268.31

Monoclinic, P21=n a= 13.151 (3) A˚ b= 7.1660 (14) A˚ c= 14.700 (3) A˚

= 97.53 (3) V= 1373.4 (5) A˚3 Z= 4

Dx= 1.298 Mg m

3 MoKradiation Cell parameters from 25

reflections

= 10–13

= 0.09 mm1 T= 293 (2) K Block, colourless 0.40.30.3 mm

Data collection

Entaf–Nonius CAD-4 diffractometer

!/2scans

2792 measured reflections 2675 independent reflections 1884 reflections withI> 2(I) R = 0.026

max= 26.0 h= 0!15 k= 0!8 l=17!17 3 standard reflections

every 200 reflections intensity decay: none

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.048} wR(F2) = 0.162 S= 1.06 2675 reflections 186 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2

(Fo2) + (0.1P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.22 e A˚ 3

min=0.19 e A˚ 3

Extinction correction:SHELXL97 Extinction coefficient: 0.091 (8)

Table 1

Selected geometric parameters (A˚ ,_). O1—C2 1.373 (2) O1—C1 1.424 (3) O2—C10 1.233 (2) N1—N2 1.416 (2)

N1—C11 1.425 (2) N1—C8 1.500 (2) N2—C10 1.332 (3)

C2—O1—C1 117.39 (17) N2—N1—C11 113.72 (15) N2—N1—C8 105.61 (14) C11—N1—C8 116.17 (15)

C10—N2—N1 114.88 (16) C10—N2—H2A 123.8 (16) N1—N2—H2A 119.2 (15)

Table 2

Hydrogen-bond geometry (A˚ ,_).

Cg3 is the centroid of the six-membered ring C11–C16.

D—H A D—H H A D A D—H A

N2—H2A O2i

0.90 (3) 1.94 (3) 2.825 (2) 169 (2) C6—H6A Cg3ii

0.93 2.65 3.558 (3) 167 C15—H15A Cg3iii 0.93 2.86 3.737 (2) 157

Symmetry codes: (i)x;yþ1;zþ1; (ii)x;y1;z; (iii)x1 2;yþ

1 2;zþ

3 2.

The H atom on N was located in a difference electron-density map and refined isotropically. H atoms on C atoms were positioned geometrically and distances to these H atoms were set at 0.93–0.98 A˚ , withUisovalues constrained to be 1.5Ueqof the parent atoms.

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97

(Sheldrick, 1990); program(s) used to refine structure:SHELXL97

(Sheldrick, 1997); molecular graphics:SHELXL97; software used to prepare material for publication:SHELXL97.

The authors thank the Centre of Test and Analysis, Nanjing University, for support.

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. Version 5.0. Enraf–Nonius, Delft, The Netherlands.

Harms, K. & Wocadlo, S. (1996).XCAD4. University of Marburg, Germany. Reddy, M. V. R. & Bell, S. C.(2003). US Patent No. WO 03 024 958. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Tanaka, K., Adachi, H. & Yamaguchi, M. (1999). JP Patent No. 11 236 376. Zhu, H.-J., Ma J., Wei, C.-M. & Wang, J.-T. (2004).Acta Cryst.E60, o411–

o413. Figure 2

supporting information

sup-1 Acta Cryst. (2005). E61, o2246–o2247

supporting information

Acta Cryst. (2005). E61, o2246–o2247 [https://doi.org/10.1107/S1600536805019227]

5-(4-Methoxyphenyl)-1-phenylpyrazolidin-3-one

Hong Shi, Hong-Jun Zhu, Peng-Wei Yin, Jin-Tang Wang and Xiao-Lan Shi

5-(4-Methoxyphenyl)-1-phenylpyrazolidin-3-one

Crystal data

C16H16N2O2

Mr = 268.31

Monoclinic, P21/n

a = 13.151 (3) Å b = 7.1660 (14) Å c = 14.700 (3) Å β = 97.53 (3)° V = 1373.4 (5) Å3

Z = 4

F(000) = 568 Dx = 1.298 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections θ = 10–13°

µ = 0.09 mm−1

T = 293 K Block, colourless 0.4 × 0.3 × 0.3 mm

Data collection

Entaf–Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

2792 measured reflections 2675 independent reflections 1884 reflections with I > 2σ(I)

Rint = 0.026

θmax = 26.0°, θmin = 2.0°

h = 0→15 k = 0→8 l = −17→17

3 standard reflections every 200 reflections intensity decay: none

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.048}

wR(F2_{) = 0.162}

S = 1.06 2675 reflections 186 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.1P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.22 e Å−3

Δρmin = −0.19 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.091 (8)

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

O1 −0.42726 (12) −0.1472 (2) 0.19555 (10) 0.0532 (5) O2 0.02326 (10) 0.2540 (2) 0.54039 (11) 0.0469 (4) N1 −0.23060 (12) 0.4101 (2) 0.51635 (11) 0.0348 (4) N2 −0.12304 (13) 0.4277 (2) 0.51878 (13) 0.0412 (5) C1 −0.4476 (2) −0.3424 (4) 0.19620 (17) 0.0600 (7)

H1A −0.4755 −0.3820 0.1357 0.090*

H1B −0.4960 −0.3681 0.2382 0.090*

H1C −0.3850 −0.4087 0.2152 0.090*

C2 −0.38687 (15) −0.0664 (3) 0.27700 (14) 0.0415 (5) C3 −0.34966 (16) 0.1142 (3) 0.27207 (14) 0.0431 (5)

H3A −0.3535 0.1743 0.2156 0.052*

C4 −0.30681 (15) 0.2052 (3) 0.35118 (14) 0.0401 (5)

H4A −0.2821 0.3262 0.3472 0.048*

C5 −0.30028 (14) 0.1190 (3) 0.43571 (13) 0.0357 (5) C6 −0.3398 (2) −0.0591 (3) 0.43935 (16) 0.0602 (7)

H6A −0.3378 −0.1177 0.4960 0.072*

C7 −0.3824 (2) −0.1534 (3) 0.36084 (17) 0.0637 (8)

H7A −0.4075 −0.2739 0.3650 0.076*

C8 −0.25044 (14) 0.2052 (3) 0.52459 (13) 0.0345 (5)

H8A −0.2956 0.1863 0.5718 0.041*

C9 −0.14450 (15) 0.1220 (3) 0.55899 (14) 0.0395 (5)

H9A −0.1383 0.0951 0.6241 0.047*

H9B −0.1329 0.0081 0.5262 0.047*

C10 −0.07017 (15) 0.2715 (3) 0.53951 (13) 0.0361 (5) C11 −0.27256 (14) 0.5280 (2) 0.58005 (13) 0.0324 (4) C12 −0.37790 (15) 0.5230 (3) 0.58120 (14) 0.0423 (5)

H12A −0.4178 0.4380 0.5444 0.051*

C13 −0.42353 (17) 0.6437 (3) 0.63674 (17) 0.0507 (6)

H13A −0.4942 0.6399 0.6366 0.061*

C14 −0.36558 (19) 0.7702 (3) 0.69259 (16) 0.0535 (6)

H14A −0.3968 0.8514 0.7298 0.064*

C15 −0.26149 (19) 0.7741 (3) 0.69224 (15) 0.0489 (6)

H15A −0.2220 0.8586 0.7297 0.059*

C16 −0.21375 (16) 0.6534 (3) 0.63662 (13) 0.0387 (5)

H16A −0.1429 0.6568 0.6374 0.046*

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sup-3 Acta Cryst. (2005). E61, o2246–o2247

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O1 0.0651 (10) 0.0495 (10) 0.0418 (9) −0.0115 (8) −0.0054 (7) −0.0009 (7) O2 0.0426 (9) 0.0337 (9) 0.0657 (10) 0.0026 (6) 0.0118 (7) −0.0014 (7) N1 0.0400 (9) 0.0225 (9) 0.0437 (9) −0.0016 (7) 0.0121 (7) −0.0008 (7) N2 0.0425 (10) 0.0236 (9) 0.0610 (11) 0.0001 (7) 0.0206 (8) 0.0033 (8) C1 0.0673 (16) 0.0536 (16) 0.0566 (15) −0.0218 (12) −0.0017 (12) −0.0070 (12) C2 0.0409 (11) 0.0393 (12) 0.0430 (11) −0.0045 (9) 0.0010 (9) −0.0006 (9) C3 0.0502 (12) 0.0418 (12) 0.0375 (11) −0.0019 (10) 0.0061 (9) 0.0073 (9) C4 0.0450 (11) 0.0288 (10) 0.0469 (12) −0.0040 (8) 0.0082 (9) 0.0056 (9) C5 0.0364 (10) 0.0268 (10) 0.0437 (11) −0.0007 (8) 0.0041 (8) 0.0027 (8) C6 0.0938 (19) 0.0400 (13) 0.0420 (12) −0.0237 (13) −0.0091 (12) 0.0117 (10) C7 0.0932 (19) 0.0399 (14) 0.0526 (14) −0.0275 (13) −0.0111 (13) 0.0073 (11) C8 0.0397 (10) 0.0231 (10) 0.0416 (11) −0.0013 (8) 0.0087 (8) 0.0031 (8) C9 0.0470 (12) 0.0270 (10) 0.0434 (11) −0.0012 (9) 0.0014 (9) 0.0024 (9) C10 0.0433 (11) 0.0275 (10) 0.0378 (11) 0.0015 (8) 0.0063 (8) −0.0025 (8) C11 0.0401 (10) 0.0215 (9) 0.0364 (10) 0.0037 (8) 0.0072 (8) 0.0046 (7) C12 0.0399 (11) 0.0366 (12) 0.0501 (12) 0.0023 (9) 0.0044 (9) 0.0022 (9) C13 0.0441 (12) 0.0493 (14) 0.0617 (14) 0.0091 (10) 0.0185 (10) 0.0058 (11) C14 0.0716 (16) 0.0413 (13) 0.0522 (13) 0.0102 (12) 0.0261 (11) −0.0014 (10) C15 0.0723 (16) 0.0332 (12) 0.0430 (12) −0.0052 (10) 0.0137 (10) −0.0051 (9) C16 0.0435 (11) 0.0290 (11) 0.0439 (11) −0.0023 (8) 0.0075 (9) 0.0022 (8)

Geometric parameters (Å, º)

O1—C2 1.373 (2) C6—C7 1.390 (3)

O1—C1 1.424 (3) C6—H6A 0.9300

O2—C10 1.233 (2) C7—H7A 0.9300

N1—N2 1.416 (2) C8—C9 1.539 (3)

N1—C11 1.425 (2) C8—H8A 0.9800

N1—C8 1.500 (2) C9—C10 1.503 (3)

N2—C10 1.332 (3) C9—H9A 0.9700

N2—H2A 0.90 (2) C9—H9B 0.9700

C1—H1A 0.9600 C11—C12 1.388 (3)

C1—H1B 0.9600 C11—C16 1.389 (3)

C1—H1C 0.9600 C12—C13 1.379 (3)

C2—C7 1.375 (3) C12—H12A 0.9300

C2—C3 1.389 (3) C13—C14 1.383 (3)

C3—C4 1.387 (3) C13—H13A 0.9300

C3—H3A 0.9300 C14—C15 1.370 (3)

C4—C5 1.380 (3) C14—H14A 0.9300

C4—H4A 0.9300 C15—C16 1.395 (3)

C5—C6 1.382 (3) C15—H15A 0.9300

C5—C8 1.514 (3) C16—H16A 0.9300

C2—O1—C1 117.39 (17) N1—C8—C9 104.26 (15)

N2—N1—C8 105.61 (14) N1—C8—H8A 108.7

C11—N1—C8 116.17 (15) C5—C8—H8A 108.7

C10—N2—N1 114.88 (16) C9—C8—H8A 108.7

C10—N2—H2A 123.8 (16) C10—C9—C8 104.17 (15)

N1—N2—H2A 119.2 (15) C10—C9—H9A 110.9

O1—C1—H1A 109.5 C8—C9—H9A 110.9

O1—C1—H1B 109.5 C10—C9—H9B 110.9

H1A—C1—H1B 109.5 C8—C9—H9B 110.9

O1—C1—H1C 109.5 H9A—C9—H9B 108.9

H1A—C1—H1C 109.5 O2—C10—N2 125.27 (18)

H1B—C1—H1C 109.5 O2—C10—C9 126.67 (18)

O1—C2—C7 123.8 (2) N2—C10—C9 108.05 (16)

O1—C2—C3 116.51 (19) C12—C11—C16 119.20 (18)

C7—C2—C3 119.7 (2) C12—C11—N1 117.75 (17)

C4—C3—C2 120.10 (19) C16—C11—N1 122.94 (17)

C4—C3—H3A 119.9 C13—C12—C11 120.2 (2)

C2—C3—H3A 119.9 C13—C12—H12A 119.9

C5—C4—C3 120.99 (19) C11—C12—H12A 119.9

C5—C4—H4A 119.5 C12—C13—C14 120.9 (2)

C3—C4—H4A 119.5 C12—C13—H13A 119.5

C4—C5—C6 117.98 (19) C14—C13—H13A 119.5

C4—C5—C8 124.26 (18) C15—C14—C13 119.0 (2)

C6—C5—C8 117.75 (18) C15—C14—H14A 120.5

C5—C6—C7 122.0 (2) C13—C14—H14A 120.5

C5—C6—H6A 119.0 C14—C15—C16 121.1 (2)

C7—C6—H6A 119.0 C14—C15—H15A 119.5

C2—C7—C6 119.3 (2) C16—C15—H15A 119.5

C2—C7—H7A 120.4 C11—C16—C15 119.6 (2)

C6—C7—H7A 120.4 C11—C16—H16A 120.2

N1—C8—C5 112.95 (16) C15—C16—H16A 120.2

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sup-5 Acta Cryst. (2005). E61, o2246–o2247

C11—N1—C8—C9 −111.37 (18) C12—C11—C16—C15 −1.2 (3) C4—C5—C8—N1 13.6 (3) N1—C11—C16—C15 175.15 (18) C6—C5—C8—N1 −167.87 (19) C14—C15—C16—C11 0.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N2—H2A···O2i _{0.90 (3) 1.94 (3) 2.825 (2) 169 (2)}

C4—H4A···N1 0.93 2.56 2.901 (3) 102

C16—H16A···N2 0.93 2.43 2.753 (3) 100

C6—H6A···Cg3ii _{0.93 2.65 3.558 (3) 167}

C15—H15A···Cg3iii _{0.93 2.86 3.737 (2) 157}