5-(3,4-Dimethoxy­phen­yl)-1-(4-methyl­phen­yl)pyrazolidin-3-one

In the mol­ecule of the title compound, C₁₈H₂₀N₂O₃, the five-membered ring adopts an envelope conformation. Intra­molecular C—H...N hydrogen bonds cause the formation of two further five-membered planar rings. In the crystal structure, inter­molecular C—H...O and N—H...·O hydrogen bonds link the mol­ecules to form a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.076
• wR factor = 0.187
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C
DIFMN02_ALERT_2_C  The minimum difference density is < -0.1*ZMAX*0.75
            _refine_diff_density_min given =     -0.746
            Test value =     -0.600
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT098_ALERT_2_C Minimum (Negative) Residual Density ............      -0.75 e/A   
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.72 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.17 Ratio
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C18
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C18 H20 N2 O3

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C9     = ...          R

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

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

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S1. Comment

Pyrazolidin-3-one derivatives 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). In the process of synthesis, we obtained the title compound, (I), and we herein report its crystal structure.

In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular C—H···N hydrogen bonds (Table 1) cause to the formation of two five-membered planar rings A (N1/C9/C6/C5/H5A) and B (N2/N1/C12/C17/H17A). The five-membered ring C (N1/N2/C9—C11) is not planar and has an envelope conformation with atom C9 is displaced by -0.470 (3) Å from the plane of the other ring atoms. D (C3—C8) and E (C12—C17) rings are, of course, planar and the dihedral angles between the planar rings are A/B = 83.84 (2)°, A/D = 1.65 (3) and B/E = 2.22 (3)°.

In the crystal structure, intermolecular C—H···O and N—H···.O hydrogen bonds (Table 1) link the molecules to form a three-dimensional network (Fig. 2). The intra- and intermolecular hydrogen bonds seem to be effective in the stabilization of the crystal structure.

Related literature

For general background, see: Menozzi et al. (1990); Brooks et al. (1990); Greenwood et al. (1995). For related literatue, see: Zhu et al. (2004). For bond- length data, see: Allen et al. (1987).

S2. Experimental

To a solution of sodium (40 mmol) in anhydrous methanol (9 ml) was added ethanolamine (4 ml) and n-butanol (20 ml). The methanol was removed by distillation and ethyl 3-(3,4-dimethoxyphenyl)acrylate (9.4 g) was added. The resulting mixture was refluxed for 1 h at 373 K, then 4-methylphenylhydrazine (4.9 g) was added. The reaction mixture was refluxed for a further 6 h, left to cool to room temperature, acidified with acetic acid (36%), allowed to stand, filtered, and the filter cake was crystallized from ethanol to give the title compound (m.p. 412 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution (Zhu et al., 2004).

S3. Refinement

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

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

5-(3,4-Dimethoxyphenyl)-1-(4-methylphenyl)pyrazolidin-3-one

Crystal data

C18H20N2O3	Z = 2
Mr = 312.36	F(000) = 332
Triclinic, P1	Dx = 1.248 Mg m^−3
Hall symbol: -P 1	Melting point: 412 K
a = 9.4290 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.107 (2) Å	Cell parameters from 25 reflections
c = 10.848 (2) Å	θ = 10–13°
α = 96.50 (3)°	µ = 0.09 mm^−1
β = 111.60 (3)°	T = 298 K
γ = 114.43 (3)°	Block, colorless
V = 831.0 (5) Å^3	0.40 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	2256 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 26.0°, θmin = 2.1°
ω/2θ scans	h = −11→10
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.965, Tmax = 0.982	l = 0→13
3477 measured reflections	3 standard reflections every 120 min
3266 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.187	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 1.3P] where P = (Fo^2 + 2Fc^2)/3
3266 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.75 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.9140 (3)	0.7698 (3)	1.6030 (3)	0.0823 (10)
O2	0.6384 (4)	0.7591 (3)	1.4264 (3)	0.0622 (7)
O3	0.4293 (3)	0.1296 (3)	0.9351 (2)	0.0507 (6)
N1	0.3685 (3)	0.0623 (3)	1.2249 (3)	0.0408 (6)
N2	0.4294 (4)	0.0539 (3)	1.1247 (3)	0.0443 (6)
H2A	0.4875	0.0072	1.1242	0.053*
C1	1.0718 (7)	0.7904 (6)	1.6861 (6)	0.102
H1A	1.1489	0.8963	1.7407	0.152*
H1B	1.1188	0.7605	1.6301	0.152*
H1C	1.0613	0.7290	1.7470	0.152*
C2	0.4899 (6)	0.7622 (4)	1.3261 (4)	0.0689 (11)
H2B	0.5106	0.8654	1.3433	0.103*
H2C	0.3871	0.6989	1.3344	0.103*
H2D	0.4729	0.7245	1.2337	0.103*
C3	0.7828 (5)	0.6260 (4)	1.5139 (4)	0.0520 (9)
C4	0.7907 (5)	0.4925 (4)	1.5148 (4)	0.0577 (9)
H4A	0.8916	0.4962	1.5785	0.069*
C5	0.6475 (4)	0.3518 (4)	1.4203 (3)	0.0471 (8)
H5A	0.6528	0.2622	1.4227	0.057*
C6	0.4998 (4)	0.3456 (3)	1.3244 (3)	0.0375 (7)
C7	0.4940 (4)	0.4819 (3)	1.3249 (3)	0.0411 (7)
H7A	0.3935	0.4783	1.2605	0.049*
C8	0.6322 (4)	0.6205 (3)	1.4175 (3)	0.0431 (7)
C9	0.3381 (4)	0.1974 (3)	1.2193 (3)	0.0397 (7)
H9A	0.2375	0.1803	1.2359	0.048*
C10	0.3897 (4)	0.1241 (3)	1.0309 (3)	0.0397 (7)
C11	0.2950 (4)	0.1966 (3)	1.0682 (3)	0.0427 (7)
H11A	0.1697	0.1369	1.0074	0.051*
H11B	0.3374	0.2998	1.0623	0.051*
C12	0.2129 (4)	−0.0769 (3)	1.1967 (3)	0.0391 (7)
C13	0.1462 (5)	−0.0834 (4)	1.2907 (4)	0.0539 (9)
H13A	0.1990	0.0017	1.3679	0.065*
C14	0.0013 (5)	−0.2156 (4)	1.2711 (4)	0.0594 (10)
H14A	−0.0435	−0.2175	1.3347	0.071*
C15	−0.0788 (4)	−0.3457 (4)	1.1586 (4)	0.0502 (8)
C16	−0.0111 (5)	−0.3373 (4)	1.0668 (4)	0.0502 (8)
H16A	−0.0639	−0.4225	0.9897	0.060*
C17	0.1349 (4)	−0.2051 (4)	1.0845 (3)	0.0441 (8)
H17A	0.1794	−0.2035	1.0208	0.053*
C18	−0.2397 (5)	−0.4880 (4)	1.1361 (5)	0.0746 (12)
H18A	−0.2765	−0.5661	1.0541	0.112*
H18B	−0.3322	−0.4651	1.1242	0.112*
H18C	−0.2130	−0.5235	1.2157	0.112*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0469 (15)	0.0648 (18)	0.084 (2)	0.0143 (13)	0.0090 (15)	−0.0226 (15)
O2	0.0804 (18)	0.0322 (12)	0.0575 (15)	0.0212 (12)	0.0256 (14)	0.0059 (11)
O3	0.0699 (16)	0.0443 (13)	0.0469 (13)	0.0281 (12)	0.0347 (12)	0.0180 (11)
N1	0.0494 (15)	0.0334 (13)	0.0480 (15)	0.0201 (12)	0.0298 (13)	0.0165 (12)
N2	0.0559 (16)	0.0431 (15)	0.0554 (17)	0.0305 (13)	0.0366 (14)	0.0250 (13)
C1	0.102	0.102	0.102	0.050	0.047	0.032
C2	0.100 (3)	0.051 (2)	0.055 (2)	0.041 (2)	0.030 (2)	0.0209 (18)
C3	0.048 (2)	0.0449 (19)	0.0448 (19)	0.0137 (16)	0.0198 (16)	−0.0044 (15)
C4	0.046 (2)	0.063 (2)	0.049 (2)	0.0275 (18)	0.0114 (17)	0.0023 (17)
C5	0.0481 (19)	0.0451 (18)	0.0462 (19)	0.0231 (16)	0.0207 (16)	0.0104 (15)
C6	0.0419 (17)	0.0340 (15)	0.0346 (15)	0.0146 (13)	0.0209 (14)	0.0088 (12)
C7	0.0492 (18)	0.0366 (16)	0.0369 (16)	0.0190 (14)	0.0218 (14)	0.0110 (13)
C8	0.0530 (19)	0.0341 (16)	0.0409 (17)	0.0168 (14)	0.0267 (16)	0.0080 (13)
C9	0.0411 (17)	0.0307 (15)	0.0463 (18)	0.0153 (13)	0.0219 (14)	0.0120 (13)
C10	0.0419 (17)	0.0282 (15)	0.0408 (17)	0.0128 (13)	0.0168 (14)	0.0086 (13)
C11	0.0457 (18)	0.0343 (16)	0.0412 (17)	0.0197 (14)	0.0143 (14)	0.0078 (13)
C12	0.0431 (17)	0.0319 (15)	0.0402 (16)	0.0164 (13)	0.0185 (14)	0.0145 (13)
C13	0.065 (2)	0.0410 (18)	0.0421 (18)	0.0117 (17)	0.0296 (17)	0.0066 (15)
C14	0.071 (2)	0.052 (2)	0.053 (2)	0.0188 (19)	0.038 (2)	0.0196 (17)
C15	0.0482 (19)	0.0357 (17)	0.055 (2)	0.0140 (15)	0.0187 (17)	0.0193 (15)
C16	0.054 (2)	0.0315 (16)	0.053 (2)	0.0182 (15)	0.0186 (17)	0.0072 (14)
C17	0.0531 (19)	0.0394 (17)	0.0467 (18)	0.0250 (15)	0.0279 (16)	0.0104 (14)
C18	0.062 (3)	0.049 (2)	0.088 (3)	0.0066 (19)	0.033 (2)	0.026 (2)

Geometric parameters (Å, º)

O1—C1	1.336 (6)	C6—C9	1.521 (4)
O1—C3	1.376 (4)	C7—C8	1.370 (4)
O2—C8	1.369 (4)	C7—H7A	0.9300
O2—C2	1.438 (5)	C9—C11	1.535 (4)
O3—C10	1.226 (4)	C9—H9A	0.9800
N1—N2	1.412 (3)	C10—C11	1.496 (4)
N1—C12	1.446 (4)	C11—H11A	0.9700
N1—C9	1.511 (4)	C11—H11B	0.9700
N2—C10	1.335 (4)	C12—C13	1.376 (4)
N2—H2A	0.8600	C12—C17	1.377 (4)
C1—H1A	0.9600	C13—C14	1.382 (5)
C1—H1B	0.9600	C13—H13A	0.9300
C1—H1C	0.9600	C14—C15	1.387 (5)
C2—H2B	0.9600	C14—H14A	0.9300
C2—H2C	0.9600	C15—C16	1.360 (5)
C2—H2D	0.9600	C15—C18	1.508 (5)
C3—C4	1.383 (5)	C16—C17	1.394 (5)
C3—C8	1.393 (5)	C16—H16A	0.9300
C4—C5	1.399 (5)	C17—H17A	0.9300
C4—H4A	0.9300	C18—H18A	0.9600
C5—C6	1.369 (4)	C18—H18B	0.9600
C5—H5A	0.9300	C18—H18C	0.9600
C6—C7	1.401 (4)
C1—O1—C3	119.4 (4)	N1—C9—C11	102.6 (2)
C8—O2—C2	117.6 (3)	C6—C9—C11	112.0 (2)
N2—N1—C12	113.3 (2)	N1—C9—H9A	110.2
N2—N1—C9	103.1 (2)	C6—C9—H9A	110.2
C12—N1—C9	112.8 (2)	C11—C9—H9A	110.2
C10—N2—N1	114.9 (2)	O3—C10—N2	125.2 (3)
C10—N2—H2A	122.6	O3—C10—C11	127.6 (3)
N1—N2—H2A	122.6	N2—C10—C11	107.2 (3)
O1—C1—H1A	109.5	C10—C11—C9	103.3 (3)
O1—C1—H1B	109.5	C10—C11—H11A	111.1
H1A—C1—H1B	109.5	C9—C11—H11A	111.1
O1—C1—H1C	109.5	C10—C11—H11B	111.1
H1A—C1—H1C	109.5	C9—C11—H11B	111.1
H1B—C1—H1C	109.5	H11A—C11—H11B	109.1
O2—C2—H2B	109.5	C13—C12—C17	118.9 (3)
O2—C2—H2C	109.5	C13—C12—N1	118.1 (3)
H2B—C2—H2C	109.5	C17—C12—N1	122.9 (3)
O2—C2—H2D	109.5	C12—C13—C14	120.4 (3)
H2B—C2—H2D	109.5	C12—C13—H13A	119.8
H2C—C2—H2D	109.5	C14—C13—H13A	119.8
O1—C3—C4	125.3 (3)	C13—C14—C15	121.4 (3)
O1—C3—C8	114.9 (3)	C13—C14—H14A	119.3
C4—C3—C8	119.8 (3)	C15—C14—H14A	119.3
C3—C4—C5	120.3 (3)	C16—C15—C14	117.4 (3)
C3—C4—H4A	119.8	C16—C15—C18	121.6 (3)
C5—C4—H4A	119.8	C14—C15—C18	121.0 (4)
C6—C5—C4	120.2 (3)	C15—C16—C17	122.1 (3)
C6—C5—H5A	119.9	C15—C16—H16A	118.9
C4—C5—H5A	119.9	C17—C16—H16A	118.9
C5—C6—C7	118.7 (3)	C12—C17—C16	119.8 (3)
C5—C6—C9	123.5 (3)	C12—C17—H17A	120.1
C7—C6—C9	117.8 (3)	C16—C17—H17A	120.1
C8—C7—C6	121.8 (3)	C15—C18—H18A	109.5
C8—C7—H7A	119.1	C15—C18—H18B	109.5
C6—C7—H7A	119.1	H18A—C18—H18B	109.5
O2—C8—C7	126.0 (3)	C15—C18—H18C	109.5
O2—C8—C3	114.9 (3)	H18A—C18—H18C	109.5
C7—C8—C3	119.1 (3)	H18B—C18—H18C	109.5
N1—C9—C6	111.6 (3)
C12—N1—N2—C10	102.0 (3)	C7—C6—C9—N1	176.2 (2)
C9—N1—N2—C10	−20.3 (3)	C5—C6—C9—C11	−120.1 (3)
C1—O1—C3—C4	9.6 (6)	C7—C6—C9—C11	61.8 (3)
C1—O1—C3—C8	−170.8 (4)	N1—N2—C10—O3	−179.6 (3)
O1—C3—C4—C5	178.9 (3)	N1—N2—C10—C11	2.1 (4)
C8—C3—C4—C5	−0.6 (5)	O3—C10—C11—C9	−161.6 (3)
C3—C4—C5—C6	1.3 (5)	N2—C10—C11—C9	16.7 (3)
C4—C5—C6—C7	−1.2 (5)	N1—C9—C11—C10	−27.6 (3)
C4—C5—C6—C9	−179.3 (3)	C6—C9—C11—C10	92.2 (3)
C5—C6—C7—C8	0.6 (4)	N2—N1—C12—C13	177.5 (3)
C9—C6—C7—C8	178.8 (3)	C9—N1—C12—C13	−65.8 (4)
C2—O2—C8—C7	−2.8 (5)	N2—N1—C12—C17	1.2 (4)
C2—O2—C8—C3	177.5 (3)	C9—N1—C12—C17	117.8 (3)
C6—C7—C8—O2	−179.7 (3)	C17—C12—C13—C14	−1.2 (5)
C6—C7—C8—C3	0.1 (5)	N1—C12—C13—C14	−177.7 (3)
O1—C3—C8—O2	0.1 (4)	C12—C13—C14—C15	1.2 (6)
C4—C3—C8—O2	179.7 (3)	C13—C14—C15—C16	−1.2 (6)
O1—C3—C8—C7	−179.6 (3)	C13—C14—C15—C18	−178.3 (4)
C4—C3—C8—C7	0.0 (5)	C14—C15—C16—C17	1.1 (5)
N2—N1—C9—C6	−91.5 (3)	C18—C15—C16—C17	178.3 (3)
C12—N1—C9—C6	146.0 (2)	C13—C12—C17—C16	1.2 (5)
N2—N1—C9—C11	28.6 (3)	N1—C12—C17—C16	177.5 (3)
C12—N1—C9—C11	−93.9 (3)	C15—C16—C17—C12	−1.2 (5)
C5—C6—C9—N1	−5.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3^i	0.86	2.00	2.836 (5)	163
C1—H1A···O3^ii	0.96	2.57	3.472 (6)	156
C13—H13A···O2^iii	0.93	2.52	3.452 (5)	176
C5—H5A···N1	0.93	2.49	2.846 (5)	103
C17—H17A···N2	0.93	2.43	2.755 (5)	101

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x+1, y+1, z+1; (iii) −x+1, −y+1, −z+3.