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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o364.
Published online 2009 January 23. doi:  10.1107/S1600536809001226
PMCID: PMC2968261

2,2′-(1-Phenyl-1H-pyrazole-3,5-di­yl)diphenol

Abstract

The title compound, C21H16N2O2, was derived from 1-(2-hydroxy­phen­yl)-3-(-methoxy­phen­yl)propane-1,3-dione. The mol­ecular structure of the title compound is stabilized by an intra­molecular O—H(...)N hydrogen bond. The dihedral angle between the hydroxy­phenyl ring involved in this intra­molecular hydrogen bond and the pyrazole ring is significantly smaller [10.07 (6)°] than the dihedral angle between the pyrazole and the other hydroxy­phenyl ring [36.64 (5)°]. The benzene ring makes a dihedral angle of 54.95 (3)° with the pyrazole ring. The crystal packing is stabilized by O—H(...)O and O—H(...)N hydrogen bonds.

Related literature

For the biological activity of pyrazoles, see: Beeam et al. (1984 [triangle]). For the preparation of new materials for medicine, see: Elguero (1983 [triangle]). For the coordination chemistry of pyrazoles, see: Bonati (1980 [triangle]). For their use as analytical reagents, see: Freyer & Radeglia (1981 [triangle]). For the synthesis of 1-(2′-hydroxy­phen­yl)-3-(2′′-methoxy­phen­yl)propane-1,3-dione, see: Ahmad et al. (1997 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o364-scheme1.jpg

Experimental

Crystal data

  • C21H16N2O2
  • M r = 328.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o364-efi1.jpg
  • a = 9.7034 (8) Å
  • b = 11.7407 (9) Å
  • c = 14.9486 (14) Å
  • β = 104.294 (7)°
  • V = 1650.3 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 173 (2) K
  • 0.48 × 0.46 × 0.46 mm

Data collection

  • Stoe IPDSII two-circle diffractometer
  • Absorption correction: none
  • 12165 measured reflections
  • 3799 independent reflections
  • 3235 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.101
  • S = 1.03
  • 3799 reflections
  • 235 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]) and XP in SHELXTL-Plus (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001226/bx2193sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001226/bx2193Isup2.hkl

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

Acknowledgments

AB is grateful to the Higher Education Commission of Pakistan for a grant.

supplementary crystallographic information

Comment

Pyrazoles are important because of their potential for biological activity. They have antipuretic, anti-inflammatory and antirheumatic effects (Beeam et al., 1984). Both traditional and new scientific methods have been used to prepare new materials for medicine (Elguero et al., 1983) and agriculture (Trofimenko, 1972). Neutral and anionic pyrazoles are excellent ligands and their co-ordination chemistry has been extensively studied (Bonati, 1980). Pyrazoles are also used as analytical reagents (Freyer et al., 1981) The molecular structure of the title compound is stabilized by an intramolecular O-H···N hydrogen bond. The dihedral angle between the hydroxyphenyl ring involved in this intramolecular hydrogen bond is significantly smaller [10.07 (6)°] than the dihedral angle between the pyrazole and the other hydroxyphenyl ring [36.64 (5)°]. The phenyl ring makes a makes dihedral angle of 54.95 (3)° with the pyrazol ring. The crystal packing is stabilized by O-H···O hydrogen bonds.

Experimental

1-(2'-hydroxyphenyl)-3-(2"-methoxyphenyl) propane-1,3-dione (I) was prepared by a modified Baker Venkataram rearrangement as reported earlier (Ahmad et al. 1997). 1-Phenyl-3,5-bis(2'-hydroxy phenyl)phyrazole(III) was synthesized by demethylation of 2-(5-(2-methoxyphenyl)-1-phenyl-1H-pyrazol-3-yl)phenol(II), which was prepared by refluxing 1-(2'-hydroxyphenyl)-3-(2"-methoxyphenyl) propane-1,3-dione (2.7 g, 10 mmol) with phenyl hydrazine (1.08 g,0.99 ml, 10 mmol) in 100 ml absolute ethanol for seven hours as shown in Fig. 3. The product was recrystallized using absolute ethanol. (yield: 90%, m.p: 473k)

Refinement

H atoms bonded to C were geometrically positioned and refined using a riding model with fixed individual displacement parameters [U(H) = 1.2 Ueq(C)] and with C—H = 0.95 Å. H atoms bonded to O were freely refined.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Part of the crystal structure of(I) showing the formation of a one-dimensional chain along [100] direction and the hydrogen-bonding and O-H···N intramolecular contact.
Fig. 3.
Preparation of the title compound.

Crystal data

C21H16N2O2F(000) = 688
Mr = 328.36Dx = 1.322 Mg m3
Monoclinic, P21/cMelting point: 473 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 9.7034 (8) ÅCell parameters from 10768 reflections
b = 11.7407 (9) Åθ = 3.6–27.6°
c = 14.9486 (14) ŵ = 0.09 mm1
β = 104.294 (7)°T = 173 K
V = 1650.3 (2) Å3Block, colourless
Z = 40.48 × 0.46 × 0.46 mm

Data collection

Stoe IPDSII two-circle diffractometer3235 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
graphiteθmax = 27.6°, θmin = 3.6°
ω scansh = −12→12
12165 measured reflectionsk = −13→15
3799 independent reflectionsl = −18→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101w = 1/[σ2(Fo2) + (0.0529P)2 + 0.3119P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3799 reflectionsΔρmax = 0.24 e Å3
235 parametersΔρmin = −0.15 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.030 (2)

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 (Å2)

xyzUiso*/Ueq
N10.72854 (9)0.56525 (9)0.70176 (6)0.0273 (2)
N20.60684 (9)0.61144 (9)0.64778 (6)0.0277 (2)
O10.34395 (9)0.66647 (10)0.57881 (6)0.0434 (3)
H10.428 (2)0.6418 (18)0.6211 (13)0.068 (6)*
O21.07930 (9)0.61561 (9)0.60415 (7)0.0416 (2)
H21.170 (2)0.6300 (17)0.5950 (13)0.073 (6)*
C30.63161 (11)0.62529 (9)0.56362 (7)0.0250 (2)
C40.76965 (11)0.58763 (10)0.56388 (7)0.0267 (2)
H40.81300.58850.51340.032*
C50.82919 (11)0.54909 (9)0.65248 (7)0.0260 (2)
C110.73784 (12)0.55181 (10)0.79885 (7)0.0293 (2)
C120.84714 (13)0.60411 (11)0.86344 (8)0.0354 (3)
H120.91700.64790.84420.042*
C130.85265 (15)0.59125 (13)0.95705 (9)0.0447 (3)
H130.92740.62571.00210.054*
C140.74906 (17)0.52810 (14)0.98457 (9)0.0479 (4)
H140.75320.51971.04840.057*
C150.63982 (16)0.47744 (13)0.91924 (9)0.0437 (3)
H150.56890.43490.93840.052*
C160.63368 (13)0.48862 (11)0.82558 (8)0.0349 (3)
H160.55930.45350.78060.042*
C310.51991 (11)0.67507 (9)0.48859 (7)0.0260 (2)
C320.38098 (12)0.69291 (11)0.49811 (8)0.0308 (2)
C330.27648 (13)0.73925 (12)0.42651 (9)0.0399 (3)
H330.18260.74920.43360.048*
C340.30899 (14)0.77093 (12)0.34478 (9)0.0409 (3)
H340.23780.80350.29620.049*
C350.44618 (15)0.75502 (12)0.33381 (8)0.0395 (3)
H350.46870.77650.27780.047*
C360.54978 (13)0.70771 (11)0.40505 (8)0.0329 (3)
H360.64310.69720.39710.040*
C510.96705 (11)0.49298 (10)0.69189 (7)0.0270 (2)
C521.08989 (12)0.52664 (10)0.66442 (8)0.0304 (2)
C531.21876 (13)0.46994 (11)0.69982 (9)0.0368 (3)
H531.30130.49270.68110.044*
C541.22731 (13)0.38090 (11)0.76202 (9)0.0385 (3)
H541.31550.34330.78560.046*
C551.10706 (14)0.34660 (11)0.78991 (8)0.0364 (3)
H551.11270.28580.83260.044*
C560.97871 (13)0.40228 (10)0.75474 (8)0.0317 (3)
H560.89670.37840.77370.038*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0242 (4)0.0347 (5)0.0222 (4)0.0020 (4)0.0044 (3)0.0012 (4)
N20.0238 (4)0.0358 (5)0.0225 (4)0.0015 (4)0.0037 (3)0.0012 (4)
O10.0252 (4)0.0723 (7)0.0332 (5)0.0042 (4)0.0082 (4)0.0121 (4)
O20.0270 (4)0.0485 (6)0.0511 (5)0.0055 (4)0.0130 (4)0.0173 (4)
C30.0258 (5)0.0271 (5)0.0216 (5)−0.0035 (4)0.0047 (4)−0.0019 (4)
C40.0270 (5)0.0299 (6)0.0235 (5)−0.0019 (4)0.0070 (4)−0.0021 (4)
C50.0248 (5)0.0268 (5)0.0266 (5)−0.0013 (4)0.0066 (4)−0.0027 (4)
C110.0312 (5)0.0343 (6)0.0222 (5)0.0058 (5)0.0065 (4)0.0023 (4)
C120.0339 (6)0.0421 (7)0.0283 (6)0.0023 (5)0.0041 (5)−0.0004 (5)
C130.0484 (7)0.0549 (9)0.0262 (6)0.0066 (6)0.0002 (5)−0.0023 (6)
C140.0656 (9)0.0546 (9)0.0243 (6)0.0107 (7)0.0127 (6)0.0059 (6)
C150.0552 (8)0.0448 (8)0.0359 (7)0.0039 (6)0.0201 (6)0.0090 (6)
C160.0371 (6)0.0373 (6)0.0313 (6)0.0017 (5)0.0102 (5)0.0028 (5)
C310.0272 (5)0.0260 (5)0.0228 (5)−0.0037 (4)0.0026 (4)−0.0019 (4)
C320.0279 (5)0.0354 (6)0.0276 (5)−0.0033 (4)0.0038 (4)0.0011 (5)
C330.0293 (6)0.0458 (7)0.0394 (7)0.0004 (5)−0.0013 (5)0.0041 (6)
C340.0420 (7)0.0379 (7)0.0337 (6)−0.0039 (5)−0.0079 (5)0.0066 (5)
C350.0506 (7)0.0385 (7)0.0261 (5)−0.0070 (6)0.0033 (5)0.0049 (5)
C360.0367 (6)0.0355 (6)0.0263 (5)−0.0038 (5)0.0071 (4)0.0005 (5)
C510.0267 (5)0.0276 (5)0.0256 (5)0.0017 (4)0.0040 (4)−0.0026 (4)
C520.0285 (5)0.0316 (6)0.0307 (5)0.0026 (4)0.0066 (4)0.0000 (5)
C530.0280 (6)0.0393 (7)0.0422 (7)0.0052 (5)0.0072 (5)−0.0010 (5)
C540.0347 (6)0.0360 (7)0.0411 (7)0.0106 (5)0.0024 (5)−0.0016 (5)
C550.0443 (7)0.0297 (6)0.0326 (6)0.0071 (5)0.0048 (5)0.0013 (5)
C560.0357 (6)0.0297 (6)0.0296 (5)0.0003 (5)0.0078 (5)−0.0020 (5)

Geometric parameters (Å, °)

N1—N21.3672 (13)C15—H150.9500
N1—C51.3740 (13)C16—H160.9500
N1—C111.4403 (13)C31—C361.4033 (15)
N2—C31.3477 (13)C31—C321.4057 (15)
O1—C321.3765 (14)C32—C331.3907 (17)
O1—H10.947 (19)C33—C341.3859 (18)
O2—C521.3666 (15)C33—H330.9500
O2—H20.94 (2)C34—C351.3935 (19)
C3—C41.4097 (15)C34—H340.9500
C3—C311.4744 (15)C35—C361.3873 (17)
C4—C51.3838 (15)C35—H350.9500
C4—H40.9500C36—H360.9500
C5—C511.4769 (15)C51—C561.4060 (16)
C11—C121.3887 (17)C51—C521.4098 (15)
C11—C161.3896 (16)C52—C531.4000 (16)
C12—C131.3953 (17)C53—C541.3878 (19)
C12—H120.9500C53—H530.9500
C13—C141.391 (2)C54—C551.3921 (19)
C13—H130.9500C54—H540.9500
C14—C151.386 (2)C55—C561.3898 (17)
C14—H140.9500C55—H550.9500
C15—C161.3928 (17)C56—H560.9500
N2—N1—C5111.28 (8)C32—C31—C3121.69 (9)
N2—N1—C11117.92 (8)O1—C32—C33117.66 (11)
C5—N1—C11130.48 (9)O1—C32—C31121.29 (10)
C3—N2—N1105.77 (8)C33—C32—C31121.04 (11)
C32—O1—H1106.6 (11)C34—C33—C32120.13 (12)
C52—O2—H2108.2 (12)C34—C33—H33119.9
N2—C3—C4110.36 (9)C32—C33—H33119.9
N2—C3—C31119.40 (9)C33—C34—C35119.98 (11)
C4—C3—C31130.24 (9)C33—C34—H34120.0
C5—C4—C3106.08 (9)C35—C34—H34120.0
C5—C4—H4127.0C36—C35—C34119.72 (11)
C3—C4—H4127.0C36—C35—H35120.1
N1—C5—C4106.50 (9)C34—C35—H35120.1
N1—C5—C51122.78 (9)C35—C36—C31121.51 (11)
C4—C5—C51130.59 (9)C35—C36—H36119.2
C12—C11—C16121.40 (11)C31—C36—H36119.2
C12—C11—N1119.95 (10)C56—C51—C52118.20 (10)
C16—C11—N1118.63 (10)C56—C51—C5121.32 (10)
C11—C12—C13118.88 (12)C52—C51—C5120.43 (10)
C11—C12—H12120.6O2—C52—C53121.84 (10)
C13—C12—H12120.6O2—C52—C51118.35 (10)
C14—C13—C12120.19 (13)C53—C52—C51119.81 (11)
C14—C13—H13119.9C54—C53—C52120.77 (11)
C12—C13—H13119.9C54—C53—H53119.6
C15—C14—C13120.23 (12)C52—C53—H53119.6
C15—C14—H14119.9C53—C54—C55120.18 (11)
C13—C14—H14119.9C53—C54—H54119.9
C14—C15—C16120.23 (13)C55—C54—H54119.9
C14—C15—H15119.9C56—C55—C54119.32 (12)
C16—C15—H15119.9C56—C55—H55120.3
C11—C16—C15119.06 (12)C54—C55—H55120.3
C11—C16—H16120.5C55—C56—C51121.72 (11)
C15—C16—H16120.5C55—C56—H56119.1
C36—C31—C32117.60 (10)C51—C56—H56119.1
C36—C31—C3120.71 (10)
C5—N1—N2—C3−0.45 (12)C4—C3—C31—C32170.94 (11)
C11—N1—N2—C3173.77 (10)C36—C31—C32—O1−178.03 (11)
N1—N2—C3—C40.08 (12)C3—C31—C32—O11.20 (17)
N1—N2—C3—C31−179.44 (9)C36—C31—C32—C331.20 (18)
N2—C3—C4—C50.30 (13)C3—C31—C32—C33−179.57 (12)
C31—C3—C4—C5179.76 (11)O1—C32—C33—C34177.90 (12)
N2—N1—C5—C40.63 (13)C31—C32—C33—C34−1.4 (2)
C11—N1—C5—C4−172.65 (11)C32—C33—C34—C350.8 (2)
N2—N1—C5—C51−175.58 (10)C33—C34—C35—C36−0.2 (2)
C11—N1—C5—C5111.14 (19)C34—C35—C36—C310.0 (2)
C3—C4—C5—N1−0.55 (12)C32—C31—C36—C35−0.55 (18)
C3—C4—C5—C51175.26 (11)C3—C31—C36—C35−179.78 (11)
N2—N1—C11—C12−121.61 (12)N1—C5—C51—C5635.52 (16)
C5—N1—C11—C1251.30 (18)C4—C5—C51—C56−139.69 (13)
N2—N1—C11—C1656.64 (15)N1—C5—C51—C52−146.91 (11)
C5—N1—C11—C16−130.45 (13)C4—C5—C51—C5237.88 (18)
C16—C11—C12—C130.84 (19)C56—C51—C52—O2−179.27 (11)
N1—C11—C12—C13179.04 (11)C5—C51—C52—O23.09 (16)
C11—C12—C13—C14−0.8 (2)C56—C51—C52—C53−0.05 (17)
C12—C13—C14—C150.1 (2)C5—C51—C52—C53−177.69 (10)
C13—C14—C15—C160.5 (2)O2—C52—C53—C54179.03 (12)
C12—C11—C16—C15−0.23 (18)C51—C52—C53—C54−0.17 (18)
N1—C11—C16—C15−178.46 (11)C52—C53—C54—C550.14 (19)
C14—C15—C16—C11−0.5 (2)C53—C54—C55—C560.10 (19)
N2—C3—C31—C36169.56 (11)C54—C55—C56—C51−0.32 (18)
C4—C3—C31—C36−9.85 (18)C52—C51—C56—C550.29 (17)
N2—C3—C31—C32−9.64 (16)C5—C51—C56—C55177.91 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.94 (2)1.81 (2)2.7524 (12)176.6 (19)
O1—H1···N20.947 (19)1.718 (19)2.5863 (12)150.9 (17)

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2193).

References

  • Ahmad, R., Malik, M. A., Zia-ul-Haq, M., Duddeek, H., Stefaniak, L. & Kowski, J. S. (1997). Monatsh. Chem.128, 633–640.
  • Beeam, C. F., Hall, H. L., Huff, A. M., Tummons, R. C. & Grady, S. A. O. (1984). J. Heteroat. Chem.21, 1897–1902.
  • Bonati, F. (1980). Chim. Ind. (Roma), 62, 323–328.
  • Elguero, J. (1983). Comprehensive Heterocyclic Chemistry, Vol. 5, Part 4A, pp. 167 and 304. Elmford, New York: Pergamon Press.
  • Freyer, W. & Radeglia, R. (1981). Monatsh. Chem.112, 105–117.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.

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