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The title compound, C23H19N3O2, a condensation product of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and o-amino­phenol, is a neutral tridentate ligand in en­amine–keto form, due to a strong intramolecular N—H...O hydrogen bond. A pair of intermolecular O—H...O hydrogen bonds link mol­ecules to give dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020299/cf6217sup1.cif
Contains datablocks I, 042302c

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020299/cf6217Isup2.hkl
Contains datablock I

CCDC reference: 202328

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.051
  • wR factor = 0.141
  • Data-to-parameter ratio = 11.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575 Calculated sin(theta_max)/wavelength = 0.5565
Yellow Alert Alert Level C:
PLAT_601 Alert C Structure Contains Solvent Accessible VOIDS of 66.00 A   3
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

A view of the molecular structure of the title compound, (I), is shown in Fig. 1. The compound was prepared from the reaction of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and o-aminophenol, forming this tridentate ligand. In the pyrazole ring, the bond lengths C1—C2, C2—C3, C3—N1, N1—N2 and N2—C1 (Table 1) lie between classical single- and double-bond lengths. The bond angles within this ring deviate by up to 4° from the 108° angle of a regular pentagon.

The bond lengths O1—C1, C2—C5, C1—C2 and C5—N3 also lie between classical single- and double-bond lengths. Atoms O1, C1, C2, C5 and N3 are essentially coplanar, the largest deviation from the mean plane being 0.020 (2) Å for C5. The dihedral angle between this mean plane and that of the pyrazoline ring is 5.05 (3)°, indicating a high degree of conjugation and electron delocalization. The dihedral angles between the first mean plane and phenyl rings C11–C16, C21–C26 and C31–C36 are 45.91 (3), 113.79 (4) and 129.96 (4)°, respectively, because of steric hindrance effects. The C11—N2—N1—C3 torsion angle is −4.7 (3)°, different from the value of 16.7 (3)° in 3-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenylpyrazol-4-ylmino)-4,4,4-trifluoro- 1-(2-thienyl)butane-1,2-dione (Wang et al., 2002). Small torsion angles for C1—C2—C5—N3 [−2.6 (4)°] and N3—C31—C32—O2 [−4.8 (4)°], show that atoms O1, N3 and O2 are in a cis conformation and can act as the coordinating atoms of a tridentate ligand.

A strong intramolecular N3—H3···O1 hydrogen bond is found (Table 2), resulting in an enamine–keto tautomeric form. Pairs of intermolecular O—H···O hydrogen bonds link molecules into centrosymmetric dimers, with the formation of a 14-membered ring (Fig. 2).

Experimental top

Ethanol solutions of 0.1 mol of PMBP and 0.1 mol of o-aminophenol were refluxed together for 4 h over a steam bath. The excess solvent was removed by evaporation and the concentrated solution was cooled in an ice bath with stirring. The title compound separated out as a cream powder, which was collected and dried in air. Bright-yellow single crystals, suitable for X-ray analysis, were obtained by slow cooling of a warmed ethanol solution, and were dried in a vacuum over CaCl2. The product is stable in air, and soluble in acetone and ethanol. Elemental analysis: calculated C 74.78, H 5.19, N 11.41%; found C 74.63, H 5.09, N 11.41%.

Refinement top

H atoms were placed geometrically and refined with riding-model constraints.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), shown with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. A centrosymmetric dimer formed by hydrogen bonds.
4-[(2-Hydroxyphenylamino)phenylmethylene]-5-methyl-2-phenyl-2H-pyrazol-3(4H)- one top
Crystal data top
C23H19N3O2F(000) = 388
Mr = 369.41Dx = 1.243 Mg m3
Triclinic, P1Melting point = 239–240 K
a = 7.267 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.150 (6) ÅCell parameters from 2764 reflections
c = 13.822 (8) Åθ = 1.7–25.1°
α = 111.794 (9)°µ = 0.08 mm1
β = 92.210 (11)°T = 293 K
γ = 105.987 (10)°Prism, yellow
V = 987.2 (10) Å30.30 × 0.25 × 0.20 mm
Z = 2
Data collection top
Bruker SMART 1000 CCD
diffractometer
1687 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
Graphite monochromatorθmax = 23.3°, θmin = 1.6°
ω scansh = 88
3405 measured reflectionsk = 1212
2830 independent reflectionsl = 915
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.141 w = 1/[σ2(Fo2) + (0.0697P)2 + 0.0157P]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max = 0.005
2830 reflectionsΔρmax = 0.17 e Å3
254 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.012 (3)
Crystal data top
C23H19N3O2γ = 105.987 (10)°
Mr = 369.41V = 987.2 (10) Å3
Triclinic, P1Z = 2
a = 7.267 (4) ÅMo Kα radiation
b = 11.150 (6) ŵ = 0.08 mm1
c = 13.822 (8) ÅT = 293 K
α = 111.794 (9)°0.30 × 0.25 × 0.20 mm
β = 92.210 (11)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
1687 reflections with I > 2σ(I)
3405 measured reflectionsRint = 0.024
2830 independent reflectionsθmax = 23.3°
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 0.98Δρmax = 0.17 e Å3
2830 reflectionsΔρmin = 0.19 e Å3
254 parameters
Special details top

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) top
xyzUiso*/Ueq
O10.0194 (3)0.6134 (2)0.72338 (15)0.0479 (6)
O20.0988 (3)0.3694 (2)0.45905 (16)0.0596 (7)
H20.08570.36060.39740.089*
N10.2391 (4)0.4939 (3)0.89890 (19)0.0480 (7)
N20.1741 (4)0.5886 (3)0.85161 (18)0.0426 (7)
N30.1779 (4)0.4046 (3)0.65675 (19)0.0470 (7)
H30.14690.47140.65180.071*
C10.0494 (4)0.5515 (3)0.7818 (2)0.0386 (8)
C20.0200 (4)0.4326 (3)0.7901 (2)0.0390 (8)
C30.1449 (4)0.4038 (3)0.8632 (2)0.0436 (8)
C40.1862 (5)0.2880 (4)0.8989 (3)0.0592 (10)
H4A0.08100.30450.95120.089*
H4B0.20000.20470.83960.089*
H4C0.30400.28100.92860.089*
C50.0970 (4)0.3621 (3)0.7285 (2)0.0393 (8)
C110.2587 (5)0.6946 (3)0.8672 (2)0.0419 (8)
C120.1411 (5)0.8204 (4)0.8751 (3)0.0552 (9)
H120.00890.83600.87400.083*
C130.2220 (6)0.9233 (4)0.8844 (3)0.0640 (10)
H130.14331.00740.88930.096*
C140.4176 (6)0.9016 (4)0.8865 (3)0.0657 (11)
H140.47140.96980.89110.098*
C150.5333 (5)0.7775 (4)0.8818 (3)0.0659 (11)
H150.66470.76330.88520.099*
C160.4541 (5)0.6723 (3)0.8719 (2)0.0537 (9)
H160.53240.58890.86840.081*
C210.1298 (4)0.2383 (3)0.7368 (2)0.0403 (8)
C220.2330 (5)0.2475 (3)0.8276 (2)0.0510 (9)
H220.28230.33080.88470.077*
C230.2623 (5)0.1306 (4)0.8324 (3)0.0622 (10)
H230.33010.13620.89320.093*
C240.1905 (6)0.0069 (4)0.7469 (3)0.0704 (11)
H240.21320.06990.74990.106*
C250.0863 (7)0.0033 (4)0.6578 (3)0.0801 (13)
H250.03590.08720.60130.120*
C260.0556 (6)0.1127 (4)0.6519 (2)0.0655 (11)
H260.01430.10590.59130.098*
C310.3075 (4)0.3579 (3)0.5865 (2)0.0408 (8)
C320.2665 (4)0.3454 (3)0.4826 (2)0.0425 (8)
C330.3932 (5)0.3112 (3)0.4130 (2)0.0530 (9)
H330.36790.30410.34420.080*
C340.5586 (5)0.2874 (4)0.4453 (3)0.0663 (11)
H340.64250.26330.39770.099*
C350.5990 (5)0.2992 (4)0.5476 (3)0.0666 (11)
H350.71000.28360.56890.100*
C360.4734 (5)0.3344 (4)0.6184 (2)0.0576 (10)
H360.50020.34220.68720.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0564 (14)0.0540 (15)0.0510 (14)0.0276 (12)0.0160 (11)0.0320 (12)
O20.0574 (16)0.0883 (19)0.0542 (14)0.0384 (14)0.0133 (11)0.0397 (13)
N10.0530 (18)0.0510 (18)0.0490 (16)0.0209 (15)0.0140 (13)0.0258 (14)
N20.0494 (17)0.0440 (17)0.0462 (15)0.0237 (14)0.0156 (13)0.0236 (13)
N30.0565 (18)0.0543 (18)0.0475 (16)0.0322 (15)0.0138 (14)0.0277 (14)
C10.0428 (19)0.041 (2)0.0360 (18)0.0173 (17)0.0048 (15)0.0170 (16)
C20.0431 (19)0.043 (2)0.0394 (17)0.0188 (17)0.0089 (15)0.0214 (15)
C30.046 (2)0.046 (2)0.0438 (19)0.0181 (18)0.0066 (16)0.0214 (16)
C40.067 (3)0.059 (2)0.073 (2)0.029 (2)0.0233 (19)0.041 (2)
C50.0400 (19)0.044 (2)0.0359 (17)0.0133 (16)0.0003 (15)0.0179 (15)
C110.047 (2)0.047 (2)0.0396 (18)0.0227 (18)0.0087 (15)0.0198 (16)
C120.054 (2)0.057 (2)0.067 (2)0.028 (2)0.0141 (18)0.0292 (19)
C130.075 (3)0.053 (3)0.076 (3)0.030 (2)0.019 (2)0.031 (2)
C140.085 (3)0.069 (3)0.064 (2)0.048 (3)0.019 (2)0.031 (2)
C150.053 (2)0.088 (3)0.066 (2)0.041 (3)0.0129 (19)0.027 (2)
C160.047 (2)0.059 (2)0.056 (2)0.021 (2)0.0078 (17)0.0191 (18)
C210.0411 (19)0.042 (2)0.0396 (19)0.0169 (17)0.0048 (15)0.0159 (16)
C220.055 (2)0.049 (2)0.054 (2)0.0219 (19)0.0020 (17)0.0218 (17)
C230.067 (3)0.074 (3)0.071 (3)0.038 (2)0.015 (2)0.045 (2)
C240.103 (3)0.053 (3)0.072 (3)0.039 (2)0.032 (2)0.031 (2)
C250.128 (4)0.043 (2)0.057 (3)0.023 (3)0.008 (2)0.010 (2)
C260.094 (3)0.051 (3)0.043 (2)0.019 (2)0.0025 (19)0.0142 (19)
C310.0436 (19)0.040 (2)0.0427 (19)0.0215 (17)0.0102 (15)0.0149 (15)
C320.044 (2)0.045 (2)0.0408 (19)0.0173 (17)0.0073 (15)0.0177 (15)
C330.058 (2)0.060 (2)0.041 (2)0.021 (2)0.0100 (17)0.0171 (17)
C340.063 (3)0.081 (3)0.056 (2)0.036 (2)0.0222 (19)0.018 (2)
C350.056 (2)0.086 (3)0.062 (2)0.040 (2)0.0091 (19)0.021 (2)
C360.059 (2)0.068 (3)0.049 (2)0.033 (2)0.0065 (18)0.0190 (18)
Geometric parameters (Å, º) top
O1—C11.278 (3)C14—H140.930
O2—C321.370 (3)C15—C161.408 (5)
O2—H20.820C15—H150.930
N1—C31.326 (4)C16—H160.930
N1—N21.423 (3)C21—C221.391 (4)
N2—C11.379 (3)C21—C261.393 (4)
N2—C111.429 (4)C22—C231.402 (4)
N3—C51.340 (4)C22—H220.930
N3—C311.437 (3)C23—C241.385 (5)
N3—H30.860C23—H230.930
C1—C21.444 (4)C24—C251.370 (5)
C2—C51.411 (4)C24—H240.930
C2—C31.449 (4)C25—C261.402 (5)
C3—C41.507 (4)C25—H250.930
C4—H4A0.960C26—H260.930
C4—H4B0.960C31—C361.392 (4)
C4—H4C0.960C31—C321.402 (4)
C5—C211.507 (4)C32—C331.382 (4)
C11—C161.381 (4)C33—C341.392 (4)
C11—C121.389 (5)C33—H330.930
C12—C131.395 (4)C34—C351.382 (5)
C12—H120.930C34—H340.930
C13—C141.378 (5)C35—C361.388 (4)
C13—H130.930C35—H350.930
C14—C151.383 (5)C36—H360.930
C32—O2—H2109.5C16—C15—H15119.7
C3—N1—N2105.6 (2)C11—C16—C15119.2 (3)
C1—N2—N1111.9 (2)C11—C16—H16120.4
C1—N2—C11127.3 (2)C15—C16—H16120.4
N1—N2—C11120.2 (2)C22—C21—C26119.6 (3)
C5—N3—C31131.2 (2)C22—C21—C5121.0 (3)
C5—N3—H3114.4C26—C21—C5119.3 (3)
C31—N3—H3114.4C21—C22—C23119.6 (3)
O1—C1—N2124.7 (3)C21—C22—H22120.2
O1—C1—C2129.8 (3)C23—C22—H22120.2
N2—C1—C2105.5 (2)C24—C23—C22120.2 (3)
C5—C2—C1122.7 (3)C24—C23—H23119.9
C5—C2—C3132.1 (3)C22—C23—H23119.9
C1—C2—C3105.0 (2)C25—C24—C23120.5 (3)
N1—C3—C2111.8 (3)C25—C24—H24119.8
N1—C3—C4118.0 (3)C23—C24—H24119.8
C2—C3—C4130.1 (3)C24—C25—C26120.0 (3)
C3—C4—H4A109.5C24—C25—H25120.0
C3—C4—H4B109.5C26—C25—H25120.0
H4A—C4—H4B109.5C21—C26—C25120.1 (3)
C3—C4—H4C109.5C21—C26—H26119.9
H4A—C4—H4C109.5C25—C26—H26119.9
H4B—C4—H4C109.5C36—C31—C32120.0 (3)
N3—C5—C2118.4 (3)C36—C31—N3123.6 (3)
N3—C5—C21118.3 (3)C32—C31—N3116.3 (2)
C2—C5—C21123.2 (3)O2—C32—C33125.1 (3)
C16—C11—C12120.3 (3)O2—C32—C31115.4 (2)
C16—C11—N2121.0 (3)C33—C32—C31119.5 (3)
C12—C11—N2118.6 (3)C32—C33—C34120.2 (3)
C11—C12—C13119.8 (3)C32—C33—H33119.9
C11—C12—H12120.1C34—C33—H33119.9
C13—C12—H12120.1C35—C34—C33120.4 (3)
C14—C13—C12120.6 (4)C35—C34—H34119.8
C14—C13—H13119.7C33—C34—H34119.8
C12—C13—H13119.7C34—C35—C36119.8 (3)
C13—C14—C15119.5 (3)C34—C35—H35120.1
C13—C14—H14120.3C36—C35—H35120.1
C15—C14—H14120.3C35—C36—C31120.1 (3)
C14—C15—C16120.7 (3)C35—C36—H36120.0
C14—C15—H15119.7C31—C36—H36120.0
C3—N1—N2—C13.8 (3)C13—C14—C15—C161.8 (5)
C3—N1—N2—C11175.3 (3)C12—C11—C16—C151.6 (5)
N1—N2—C1—O1174.9 (3)N2—C11—C16—C15176.7 (3)
C11—N2—C1—O14.2 (5)C14—C15—C16—C110.2 (5)
N1—N2—C1—C24.5 (3)N3—C5—C21—C22115.1 (3)
C11—N2—C1—C2175.2 (3)C2—C5—C21—C2267.2 (4)
O1—C1—C2—C50.8 (5)N3—C5—C21—C2664.8 (4)
N2—C1—C2—C5178.6 (3)C2—C5—C21—C26113.0 (4)
O1—C1—C2—C3176.0 (3)C26—C21—C22—C230.4 (5)
N2—C1—C2—C33.3 (3)C5—C21—C22—C23179.5 (3)
N2—N1—C3—C21.5 (3)C21—C22—C23—C240.6 (5)
N2—N1—C3—C4179.1 (3)C22—C23—C24—C251.6 (6)
C5—C2—C3—N1175.7 (3)C23—C24—C25—C261.5 (6)
C1—C2—C3—N11.1 (3)C22—C21—C26—C250.5 (5)
C5—C2—C3—C41.5 (6)C5—C21—C26—C25179.4 (3)
C1—C2—C3—C4176.2 (3)C24—C25—C26—C210.5 (6)
C31—N3—C5—C2177.3 (3)C5—N3—C31—C3647.9 (5)
C31—N3—C5—C214.8 (5)C5—N3—C31—C32136.5 (3)
C1—C2—C5—N32.6 (4)C36—C31—C32—O2179.4 (3)
C3—C2—C5—N3171.2 (3)N3—C31—C32—O24.8 (4)
C1—C2—C5—C21179.7 (3)C36—C31—C32—C330.8 (5)
C3—C2—C5—C216.5 (5)N3—C31—C32—C33175.0 (3)
C1—N2—C11—C16133.0 (3)O2—C32—C33—C34179.2 (3)
N1—N2—C11—C1637.0 (4)C31—C32—C33—C341.0 (5)
C1—N2—C11—C1245.3 (4)C32—C33—C34—C350.8 (6)
N1—N2—C11—C12144.7 (3)C33—C34—C35—C360.3 (6)
C16—C11—C12—C131.9 (5)C34—C35—C36—C310.1 (6)
N2—C11—C12—C13176.4 (3)C32—C31—C36—C350.3 (5)
C11—C12—C13—C140.3 (5)N3—C31—C36—C35175.1 (3)
C12—C13—C14—C151.5 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O10.862.012.750 (3)143
O2—H2···O1i0.821.962.724 (3)155
Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC23H19N3O2
Mr369.41
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.267 (4), 11.150 (6), 13.822 (8)
α, β, γ (°)111.794 (9), 92.210 (11), 105.987 (10)
V3)987.2 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3405, 2830, 1687
Rint0.024
θmax (°)23.3
(sin θ/λ)max1)0.557
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.141, 0.98
No. of reflections2830
No. of parameters254
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.19

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
O1—C11.278 (3)N3—C51.340 (4)
N1—C31.326 (4)C1—C21.444 (4)
N1—N21.423 (3)C2—C51.411 (4)
N2—C11.379 (3)C2—C31.449 (4)
C3—N1—N2105.6 (2)C1—C2—C3105.0 (2)
C1—N2—N1111.9 (2)N1—C3—C2111.8 (3)
N2—C1—C2105.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O10.862.012.750 (3)143
O2—H2···O1i0.821.962.724 (3)155
Symmetry code: (i) x, y+1, z+1.
 

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