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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1123.
Published online 2010 April 21. doi:  10.1107/S1600536810013723
PMCID: PMC2979282

(4Z)-4-[(Cyclo­propyl­amino)(phen­yl)methyl­ene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Abstract

In the title compound, C20H19N3O, the dihedral angles formed by the pyrazolone ring with the two phenyl rings are 64.27 (6) and 17.00 (6)°. The mol­ecular structure is stabilized by intra­molecular N—H(...)O and C—H(...)O hydrogen bonds. In the crystal, the mol­ecules are linked into chains along the b axis by inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the anti­bacterial, biological and analgesic activity of metal complexes of 1-phenyl-3-methyl-4-benzoyl­pyrazolon-5-one, see: Li et al. (1997 [triangle]); Liu et al. (1980 [triangle]); Zhou et al. (1999 [triangle]). For a related structure, see: Wang et al. (2003 [triangle]).

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Object name is e-66-o1123-scheme1.jpg

Experimental

Crystal data

  • C20H19N3O
  • M r = 317.38
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1123-efi1.jpg
  • a = 8.9790 (18) Å
  • b = 18.500 (4) Å
  • c = 20.050 (4) Å
  • V = 3330.5 (12) Å3
  • Z = 8
  • Cu Kα radiation
  • μ = 0.63 mm−1
  • T = 113 K
  • 0.24 × 0.21 × 0.20 mm

Data collection

  • Rigaku Saturn70 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.863, T max = 0.884
  • 34928 measured reflections
  • 3262 independent reflections
  • 2946 reflections with I > 2σ(I)
  • R int = 0.060

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.104
  • S = 1.06
  • 3262 reflections
  • 222 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: CrystalStructure (Rigaku, 2005 [triangle]); software used to prepare material for publication: CrystalStructure.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013723/ci5077sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013723/ci5077Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

1-Phenyl-3-methyl-4-benzoylpyrazolon-5-one (HPMBP), an effective β-diketonate, is widely used and well known for its extractive ability. In recent years, HPMBP and its metal complexes have also been found to have good antibacterial and biological properties. Its metal complexes have analgesic activity (Liu et al., 1980; Li et al., 1997; Zhou et al., 1999). In order to develop new medicines, we have synthesized the title compound and its crystal structure is reported here.

The structure of the title molecule is shown in Fig. 1. The dihedral angles formed by the pyrazolone ring with the C6–C11 and C15–C20 phenyl rings and cyclopropane ring are 64.27 (6)°, 17.00 (6)° and 71.28 (11)°, respectively. The O atom of the 3-methyl-1-phenylpyrazol-5-one moiety and the N atom of the amino group are available for coordination with metals. Atoms O1, C1, C2, C5 and N3 are coplanar (r.m.s. deviation = 0.028 Å). The dihedral angle between this plane and the pyrazoline ring is 4.34 (7)°, close to the value of 3.56 (3)° found in 4-{[3,4-dihydro-5-methyl-3-oxo-2-phenyl-2H-pyrazol-4-ylidene(phenyl) methylamino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (Wang et al., 2003). The bond lengths within this part of the molecule lie between classical single- and double-bond lengths, indicating extensive conjugation. A strong intramolecular N3—H1···O1 hydrogen bond (Table 1) is observed, leading to a keto-enamine form. The molecule is further stabilized by a C—H···O weak intramolecular hydrogen bond (Table 1).

The crystal structure also involves weak intermolecular C—H···O hydrogen-bond interactions (Fig. 2).

Experimental

The title compound was synthesized by refluxing a mixture of 1-phenyl-3- methyl-4-benzoylpyrazol-5-one (10 mmol) and cyclopropanamine (10 mmol) in ethanol (80 ml) over a steam bath for about 16 h. Excess solvent was removed by evaporation and the solution was cooled to room temperature. After 2 d, a colourless solid was obtained and this was dried in air. The product was recrystallized from ethanol, to afford colourless crystals of the title compound suitable for X-ray analysis.

Refinement

C-bonded H atoms were positioned geometrically, with C–H = 0.95–1.00 Å and the amine H atom (H1) was found in a difference map. The amine H atom was refined freely, while C-bonded H atoms were included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(CH2 and CH) or 1.5Ueq(CH3).

Figures

Fig. 1.
Molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. The dashed line indicates a hydrogen bond.
Fig. 2.
Part of hydrogen-bonded (dashed line) chains in the title compound.

Crystal data

C20H19N3OF(000) = 1344
Mr = 317.38Dx = 1.266 Mg m3
Orthorhombic, PbcaCu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ac 2abCell parameters from 2126 reflections
a = 8.9790 (18) Åθ = 2.2–45.5°
b = 18.500 (4) ŵ = 0.63 mm1
c = 20.050 (4) ÅT = 113 K
V = 3330.5 (12) Å3Prism, colourless
Z = 80.24 × 0.21 × 0.20 mm

Data collection

Rigaku Saturn70 diffractometer3262 independent reflections
Radiation source: fine-focus sealed tube2946 reflections with I > 2σ(I)
graphiteRint = 0.060
ω scansθmax = 72.5°, θmin = 4.4°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)h = −8→10
Tmin = 0.863, Tmax = 0.884k = −22→22
34928 measured reflectionsl = −24→24

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0583P)2 + 0.7718P] where P = (Fo2 + 2Fc2)/3
3262 reflections(Δ/σ)max = 0.001
222 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.24 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O10.67690 (13)0.11712 (5)0.26555 (4)0.0415 (3)
N10.73850 (11)0.08273 (5)0.15606 (5)0.0274 (2)
N20.82349 (11)0.02871 (5)0.12501 (5)0.0262 (2)
N30.79592 (14)0.02403 (5)0.35244 (5)0.0336 (3)
C10.73711 (15)0.07497 (6)0.22477 (6)0.0299 (3)
C20.82015 (14)0.00961 (6)0.23704 (5)0.0266 (3)
C30.87030 (13)−0.01421 (6)0.17276 (5)0.0248 (2)
C40.96427 (14)−0.07788 (7)0.15470 (6)0.0313 (3)
H4A0.9070−0.12240.16130.038*
H4B1.0531−0.07890.18310.038*
H4C0.9944−0.07420.10790.038*
C50.84118 (13)−0.01694 (6)0.30210 (5)0.0260 (3)
C60.90512 (12)−0.08952 (6)0.31601 (5)0.0246 (2)
C71.03261 (14)−0.09759 (8)0.35553 (6)0.0344 (3)
H71.0806−0.05620.37360.041*
C81.08875 (16)−0.16611 (9)0.36826 (7)0.0454 (4)
H81.1754−0.17150.39500.054*
C91.01929 (17)−0.22661 (8)0.34232 (7)0.0465 (4)
H91.0586−0.27330.35120.056*
C100.89239 (16)−0.21934 (7)0.30344 (6)0.0379 (3)
H100.8443−0.26100.28600.045*
C110.83581 (13)−0.15080 (6)0.29005 (6)0.0269 (3)
H110.7495−0.14580.26310.032*
C120.78672 (15)0.00510 (6)0.42190 (6)0.0319 (3)
H120.7987−0.04720.43310.038*
C130.84272 (17)0.05784 (9)0.47193 (6)0.0446 (4)
H13A0.88990.03840.51280.053*
H13B0.88630.10350.45520.053*
C140.68020 (16)0.04703 (8)0.46359 (6)0.0378 (3)
H14A0.62260.08600.44170.045*
H14B0.62630.02090.49930.045*
C150.67274 (13)0.13754 (6)0.11655 (6)0.0269 (3)
C160.72259 (13)0.14729 (6)0.05108 (6)0.0290 (3)
H160.80040.11800.03380.035*
C170.65736 (14)0.20020 (7)0.01143 (6)0.0346 (3)
H170.69030.2064−0.03320.042*
C180.54501 (15)0.24393 (7)0.03623 (7)0.0369 (3)
H180.50170.28030.00900.044*
C190.49628 (15)0.23398 (7)0.10137 (7)0.0364 (3)
H190.41940.26390.11850.044*
C200.55835 (14)0.18084 (6)0.14184 (6)0.0322 (3)
H200.52340.17410.18610.039*
H10.7554 (18)0.0673 (10)0.3395 (8)0.048 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0784 (7)0.0231 (4)0.0230 (4)0.0114 (4)0.0030 (4)−0.0021 (3)
N10.0387 (6)0.0230 (5)0.0204 (5)0.0014 (4)−0.0011 (4)−0.0008 (3)
N20.0302 (5)0.0259 (5)0.0226 (5)−0.0004 (4)−0.0001 (4)−0.0016 (4)
N30.0610 (7)0.0201 (5)0.0197 (5)−0.0004 (4)−0.0005 (4)0.0003 (4)
C10.0472 (7)0.0215 (5)0.0210 (5)−0.0018 (5)−0.0007 (5)−0.0012 (4)
C20.0376 (6)0.0207 (5)0.0216 (6)−0.0036 (4)−0.0013 (4)−0.0009 (4)
C30.0266 (6)0.0253 (5)0.0225 (5)−0.0039 (4)−0.0013 (4)−0.0006 (4)
C40.0315 (6)0.0358 (6)0.0267 (6)0.0052 (5)0.0025 (5)0.0019 (5)
C50.0341 (6)0.0221 (5)0.0217 (5)−0.0075 (4)−0.0014 (4)−0.0011 (4)
C60.0268 (6)0.0264 (5)0.0204 (5)−0.0019 (4)0.0012 (4)0.0017 (4)
C70.0273 (6)0.0524 (8)0.0235 (5)−0.0080 (5)−0.0008 (5)0.0058 (5)
C80.0305 (7)0.0732 (10)0.0325 (7)0.0154 (6)0.0044 (5)0.0204 (7)
C90.0528 (9)0.0464 (8)0.0403 (7)0.0257 (7)0.0173 (6)0.0171 (6)
C100.0528 (8)0.0255 (6)0.0353 (6)0.0064 (5)0.0129 (6)0.0016 (5)
C110.0297 (6)0.0241 (5)0.0269 (6)−0.0004 (4)0.0018 (4)−0.0016 (4)
C120.0509 (8)0.0256 (6)0.0191 (5)−0.0011 (5)0.0004 (5)0.0013 (4)
C130.0500 (8)0.0613 (9)0.0223 (6)−0.0220 (7)0.0007 (5)−0.0058 (6)
C140.0435 (8)0.0431 (7)0.0268 (6)0.0033 (6)0.0029 (5)0.0014 (5)
C150.0332 (6)0.0225 (5)0.0249 (5)−0.0050 (4)−0.0058 (4)−0.0005 (4)
C160.0289 (6)0.0309 (6)0.0273 (6)−0.0038 (4)−0.0025 (4)0.0033 (5)
C170.0336 (7)0.0391 (7)0.0310 (6)−0.0064 (5)−0.0050 (5)0.0102 (5)
C180.0370 (7)0.0328 (6)0.0410 (7)−0.0004 (5)−0.0110 (5)0.0084 (5)
C190.0372 (7)0.0323 (6)0.0397 (7)0.0035 (5)−0.0076 (5)−0.0035 (5)
C200.0394 (7)0.0293 (6)0.0280 (6)−0.0006 (5)−0.0035 (5)−0.0033 (5)

Geometric parameters (Å, °)

O1—C11.2525 (15)C9—H90.95
N1—C11.3852 (15)C10—C111.3921 (17)
N1—N21.4029 (13)C10—H100.95
N1—C151.4158 (14)C11—H110.95
N2—C31.3130 (15)C12—C131.4869 (17)
N3—C51.3260 (15)C12—C141.4885 (18)
N3—C121.4382 (15)C12—H121.00
N3—H10.917 (18)C13—C141.482 (2)
C1—C21.4417 (16)C13—H13A0.99
C2—C51.4066 (15)C13—H13B0.99
C2—C31.4345 (15)C14—H14A0.99
C3—C41.4935 (16)C14—H14B0.99
C4—H4A0.98C15—C201.3978 (17)
C4—H4B0.98C15—C161.3984 (17)
C4—H4C0.98C16—C171.3904 (17)
C5—C61.4868 (16)C16—H160.95
C6—C111.3940 (16)C17—C181.3854 (19)
C6—C71.4001 (16)C17—H170.95
C7—C81.388 (2)C18—C191.3898 (19)
C7—H70.95C18—H180.95
C8—C91.383 (2)C19—C201.3912 (17)
C8—H80.95C19—H190.95
C9—C101.387 (2)C20—H200.95
C1—N1—N2111.86 (9)C10—C11—C6120.38 (12)
C1—N1—C15128.83 (10)C10—C11—H11119.8
N2—N1—C15119.26 (9)C6—C11—H11119.8
C3—N2—N1106.35 (9)N3—C12—C13118.30 (11)
C5—N3—C12127.99 (10)N3—C12—C14116.99 (11)
C5—N3—H1113.9 (10)C13—C12—C1459.76 (9)
C12—N3—H1117.6 (10)N3—C12—H12116.6
O1—C1—N1126.06 (11)C13—C12—H12116.6
O1—C1—C2129.34 (11)C14—C12—H12116.6
N1—C1—C2104.59 (10)C14—C13—C1260.17 (9)
C5—C2—C3133.14 (11)C14—C13—H13A117.8
C5—C2—C1121.37 (10)C12—C13—H13A117.8
C3—C2—C1105.47 (9)C14—C13—H13B117.8
N2—C3—C2111.64 (10)C12—C13—H13B117.8
N2—C3—C4118.76 (10)H13A—C13—H13B114.9
C2—C3—C4129.60 (10)C13—C14—C1260.07 (9)
C3—C4—H4A109.5C13—C14—H14A117.8
C3—C4—H4B109.5C12—C14—H14A117.8
H4A—C4—H4B109.5C13—C14—H14B117.8
C3—C4—H4C109.5C12—C14—H14B117.8
H4A—C4—H4C109.5H14A—C14—H14B114.9
H4B—C4—H4C109.5C20—C15—C16120.12 (11)
N3—C5—C2117.73 (11)C20—C15—N1120.92 (10)
N3—C5—C6119.45 (10)C16—C15—N1118.95 (11)
C2—C5—C6122.76 (10)C17—C16—C15119.52 (12)
C11—C6—C7119.31 (11)C17—C16—H16120.2
C11—C6—C5119.47 (10)C15—C16—H16120.2
C7—C6—C5121.21 (10)C18—C17—C16120.84 (12)
C8—C7—C6119.90 (12)C18—C17—H17119.6
C8—C7—H7120.0C16—C17—H17119.6
C6—C7—H7120.0C17—C18—C19119.29 (11)
C9—C8—C7120.41 (13)C17—C18—H18120.4
C9—C8—H8119.8C19—C18—H18120.4
C7—C8—H8119.8C18—C19—C20121.04 (12)
C8—C9—C10120.22 (12)C18—C19—H19119.5
C8—C9—H9119.9C20—C19—H19119.5
C10—C9—H9119.9C19—C20—C15119.19 (12)
C9—C10—C11119.77 (13)C19—C20—H20120.4
C9—C10—H10120.1C15—C20—H20120.4
C11—C10—H10120.1
C1—N1—N2—C32.41 (13)C2—C5—C6—C7122.97 (13)
C15—N1—N2—C3179.94 (10)C11—C6—C7—C80.19 (17)
N2—N1—C1—O1176.20 (12)C5—C6—C7—C8179.28 (11)
C15—N1—C1—O1−1.0 (2)C6—C7—C8—C9−0.20 (19)
N2—N1—C1—C2−3.16 (13)C7—C8—C9—C10−0.2 (2)
C15—N1—C1—C2179.61 (11)C8—C9—C10—C110.60 (19)
O1—C1—C2—C51.6 (2)C9—C10—C11—C6−0.61 (18)
N1—C1—C2—C5−179.04 (10)C7—C6—C11—C100.21 (17)
O1—C1—C2—C3−176.70 (13)C5—C6—C11—C10−178.89 (11)
N1—C1—C2—C32.63 (13)C5—N3—C12—C13135.28 (14)
N1—N2—C3—C2−0.57 (13)C5—N3—C12—C14−156.29 (13)
N1—N2—C3—C4179.70 (10)N3—C12—C13—C14106.42 (13)
C5—C2—C3—N2−179.36 (12)N3—C12—C14—C13−108.60 (13)
C1—C2—C3—N2−1.32 (13)C1—N1—C15—C20−19.43 (18)
C5—C2—C3—C40.3 (2)N2—N1—C15—C20163.52 (10)
C1—C2—C3—C4178.36 (11)C1—N1—C15—C16161.44 (12)
C12—N3—C5—C2170.89 (12)N2—N1—C15—C16−15.61 (15)
C12—N3—C5—C6−6.43 (19)C20—C15—C16—C17−0.12 (17)
C3—C2—C5—N3170.75 (13)N1—C15—C16—C17179.02 (10)
C1—C2—C5—N3−7.04 (17)C15—C16—C17—C180.82 (18)
C3—C2—C5—C6−12.0 (2)C16—C17—C18—C19−0.70 (19)
C1—C2—C5—C6170.18 (11)C17—C18—C19—C20−0.11 (19)
N3—C5—C6—C11119.23 (13)C18—C19—C20—C150.80 (19)
C2—C5—C6—C11−57.95 (16)C16—C15—C20—C19−0.68 (17)
N3—C5—C6—C7−59.85 (16)N1—C15—C20—C19−179.80 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H1···O10.92 (2)1.88 (2)2.6726 (15)143 (2)
C20—H20···O10.952.362.9453 (16)120
C10—H10···O1i0.952.303.1809 (17)154

Symmetry codes: (i) −x+3/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5077).

References

  • Li, J.-Z., Yu, W.-J. & Du, X.-Y. (1997). Chin. J. Appl. Chem.14, 98–100.
  • Liu, J.-M., Yang, R.-D. & Ma, T.-R. (1980). Chem. J. Chin. Univ.1, 23–29.
  • Rigaku (2005). CrystalClear and CrystalStructure Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, J.-L., Yang, Y., Zhang, X. & Miao, F.-M. (2003). Acta Cryst. E59, o430–o432.
  • Zhou, Y.-P., Yang, Zh.-Y., Yu, H.-J. & Yang, R.-D. (1999). Chin. J. Appl. Chem.16, 37–41.

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