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The title compound, C21H16N2O2, was derived from 1-(2-hydroxy­phen­yl)-3-(4-methoxy­phen­yl)propane-1,3-dione. The pyrazole ring and one of the hydr­oxy-substituted benzene rings are approximately coplanar, forming a dihedral angle of 7.5 (3)°. The relative conformation of these rings may be influenced by an intra­molecular O—H...N hydrogen bond. In the crystal structure, inter­molecular O—H...O hydrogen bonds involving different hydr­oxy groups of symmetry-related mol­ecules form extended chains along [201].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808017054/lh2632sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536808017054/lh2632Isup2.hkl
Contains datablock I

CCDC reference: 696537

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.047
  • wR factor = 0.129
  • Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 300 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Pyrazoles are important because of their potential for biological activity (Beeam et al., 1984). Both traditional and new scientific methods have been used used to prepare new materials for medicine (Elguero et al., 1983) and agriculture (Trofinenko, 1972). Neutral and anionic pyrazoles are excellent ligands and their co-ordination chemistry has been extensively studied (Bonati, 1980). In the molecular structure of the title compound (III) (Fig. 1 and Fig. 3) there is an intramolecular hydrogen bond between the OH group of one phenolic group and the N atom of the pyrazole group (see Table 1 for hydrogen bond details). One of the phenyl groups is approximately coplanar with the pyrazole groups (dihedral angle = 7.5 (3)°), possibly due to the intramolecular hydrogen bond formation. The other two phenyl groups are rotated by 66.4 (12)°. In the crystal structure an intermolecular hydrogen bond between non equivalent hydroxy groups of symmetry related molecules, forms extended chains along [201] (Fig. 2).

Related literature top

For related literature, see: Ahmad et al. (1990, 1997); Beeam et al. (1984); Elguero (1983); Trofinenko (1972).

Experimental top

Compound (I) [see Fig. 3] was prepared by a modified Baker Venkataram rearrangement as reported earlier (Ahmad et al., 1990, 1997). Purification was carried out by recrystallization using absolute ethanol. Compound (II) was synthesized by adding 0.1 mole of phenyl hydrazine in 0.1 mole of compound (II) dissolved in 200 ml of absolute ethanol. The mixture was refluxed for 7 h. Solvent was removed under reduced pressure. Highly viscous residue was recrystallized using absolute ethanol. Compound (III) was synthesized by demethylation of compound (II) using 48% hydrogen bromide in acetic acid. Single crystals suitable for X-ray analysis were obtained by recrystallization from an ethanol solution of (III) at room temperature (Yield: 96%, m.p: 490K).

Refinement top

All H atoms were placed in idealized positions and treated as riding atoms, with C—H = 0.93Å, O-H = 0.82Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).

Computing details top

Data collection: XSCANS (Siemens, 1999); cell refinement: XSCANS (Siemens, 1999); data reduction: XSCANS (Siemens, 1999); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (III) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Part of the crystal structure of (III) showing the hydrogen bonds as dashed lines.
[Figure 3] Fig. 3. Reaction scheme.
2-[5-(4-Hydroxyphenyl)-1-phenyl-1H-pyrazol-3-yl]phenol top
Crystal data top
C21H16N2O2F(000) = 688
Mr = 328.36Dx = 1.336 Mg m3
Monoclinic, P21/cMelting point: 490 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.793 (3) ÅCell parameters from 84 reflections
b = 12.948 (3) Åθ = 4.6–12.4°
c = 11.705 (3) ŵ = 0.09 mm1
β = 93.508 (14)°T = 298 K
V = 1632.7 (7) Å3Prismatic, colourless
Z = 40.44 × 0.40 × 0.26 mm
Data collection top
Siemens P4
diffractometer
Rint = 0.024
Radiation source: fine-focus sealed tubeθmax = 27.5°, θmin = 1.9°
Graphite monochromatorh = 144
2θ/ω scansk = 161
5767 measured reflectionsl = 1515
3720 independent reflections3 standard reflections every 97 reflections
2353 reflections with I > 2σ(I) intensity decay: 3.7%
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)] = 0.047H-atom parameters constrained
wR(F2) = 0.128 w = 1/[σ2(Fo2) + (0.0468P)2 + 0.4416P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3720 reflectionsΔρmax = 0.15 e Å3
227 parametersΔρmin = 0.16 e Å3
0 restraintsExtinction correction: SHELXTL-Plus (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0155 (18)
Crystal data top
C21H16N2O2V = 1632.7 (7) Å3
Mr = 328.36Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.793 (3) ŵ = 0.09 mm1
b = 12.948 (3) ÅT = 298 K
c = 11.705 (3) Å0.44 × 0.40 × 0.26 mm
β = 93.508 (14)°
Data collection top
Siemens P4
diffractometer
Rint = 0.024
5767 measured reflections3 standard reflections every 97 reflections
3720 independent reflections intensity decay: 3.7%
2353 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.128H-atom parameters constrained
S = 1.03Δρmax = 0.15 e Å3
3720 reflectionsΔρmin = 0.16 e Å3
227 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.19429 (12)0.33852 (11)0.38082 (11)0.0598 (4)
H1B0.26270.31970.36210.090*
O20.55378 (12)0.16872 (10)0.17109 (13)0.0603 (4)
H2B0.50540.20640.13390.090*
N10.26395 (13)0.27005 (12)0.01205 (13)0.0467 (4)
N20.34918 (13)0.21948 (12)0.05691 (13)0.0462 (4)
C10.3431 (2)0.43942 (17)0.05478 (19)0.0628 (6)
H1A0.40750.40860.09150.075*
C20.3343 (3)0.54518 (19)0.0493 (2)0.0775 (7)
H2A0.39330.58630.08210.093*
C30.2391 (2)0.58993 (18)0.0041 (2)0.0721 (7)
H3A0.23260.66150.00640.087*
C40.1531 (2)0.53006 (17)0.0543 (2)0.0653 (6)
H4A0.08910.56100.09150.078*
C50.16142 (18)0.42387 (16)0.04968 (17)0.0546 (5)
H5A0.10350.38270.08370.066*
C60.25650 (16)0.38005 (14)0.00589 (15)0.0460 (4)
C70.21875 (16)0.10653 (14)0.03158 (15)0.0437 (4)
H7A0.18150.04440.05400.052*
C80.18333 (15)0.20293 (15)0.06634 (15)0.0433 (4)
C90.08425 (15)0.23722 (14)0.14967 (15)0.0441 (4)
C100.03190 (17)0.19422 (15)0.15016 (17)0.0523 (5)
H10A0.04740.14280.09750.063*
C110.12620 (17)0.22564 (16)0.22714 (17)0.0543 (5)
H11A0.20410.19500.22660.065*
C120.10491 (16)0.30191 (14)0.30416 (15)0.0460 (4)
C130.01140 (17)0.34379 (16)0.30736 (16)0.0516 (5)
H13A0.02690.39410.36140.062*
C140.10531 (17)0.31154 (16)0.23075 (16)0.0507 (5)
H14A0.18410.34020.23370.061*
C150.32262 (15)0.11962 (14)0.04482 (14)0.0407 (4)
C160.40064 (15)0.04285 (14)0.10482 (14)0.0404 (4)
C170.36890 (17)0.06076 (15)0.10014 (15)0.0476 (4)
H17A0.29550.08040.06030.057*
C180.44262 (18)0.13518 (16)0.15259 (17)0.0554 (5)
H18A0.42010.20440.14710.066*
C190.55033 (18)0.10638 (17)0.21343 (16)0.0546 (5)
H19A0.60000.15630.25030.066*
C200.58441 (18)0.00551 (16)0.21988 (16)0.0525 (5)
H20A0.65720.01330.26130.063*
C210.51143 (16)0.06923 (14)0.16520 (15)0.0447 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0470 (8)0.0663 (9)0.0638 (8)0.0073 (7)0.0160 (6)0.0117 (7)
O20.0474 (8)0.0503 (8)0.0796 (10)0.0043 (6)0.0253 (7)0.0134 (7)
N10.0380 (8)0.0451 (9)0.0548 (9)0.0054 (7)0.0141 (7)0.0037 (7)
N20.0375 (8)0.0480 (9)0.0514 (8)0.0067 (7)0.0119 (7)0.0054 (7)
C10.0587 (13)0.0636 (14)0.0668 (13)0.0021 (11)0.0084 (10)0.0014 (11)
C20.0867 (18)0.0632 (15)0.0824 (16)0.0137 (14)0.0036 (14)0.0141 (13)
C30.0878 (18)0.0479 (12)0.0775 (15)0.0045 (12)0.0202 (14)0.0046 (11)
C40.0574 (13)0.0601 (13)0.0764 (14)0.0163 (11)0.0138 (11)0.0140 (11)
C50.0446 (10)0.0554 (12)0.0631 (12)0.0036 (9)0.0028 (9)0.0045 (10)
C60.0423 (10)0.0457 (10)0.0483 (10)0.0043 (8)0.0104 (8)0.0023 (8)
C70.0368 (9)0.0468 (10)0.0467 (9)0.0006 (8)0.0051 (7)0.0039 (8)
C80.0324 (8)0.0524 (10)0.0443 (9)0.0035 (8)0.0032 (7)0.0031 (8)
C90.0348 (9)0.0504 (10)0.0460 (9)0.0036 (8)0.0063 (7)0.0021 (8)
C100.0423 (10)0.0558 (11)0.0572 (11)0.0031 (9)0.0089 (8)0.0118 (9)
C110.0363 (9)0.0598 (12)0.0651 (12)0.0072 (9)0.0108 (9)0.0073 (10)
C120.0400 (9)0.0490 (10)0.0475 (10)0.0079 (8)0.0103 (8)0.0008 (8)
C130.0477 (11)0.0601 (12)0.0465 (10)0.0009 (9)0.0014 (8)0.0095 (9)
C140.0359 (9)0.0654 (12)0.0500 (10)0.0050 (9)0.0021 (8)0.0021 (9)
C150.0351 (9)0.0465 (10)0.0400 (8)0.0025 (8)0.0022 (7)0.0052 (8)
C160.0344 (8)0.0487 (10)0.0375 (8)0.0031 (8)0.0034 (7)0.0033 (7)
C170.0415 (10)0.0524 (11)0.0478 (10)0.0047 (8)0.0051 (8)0.0032 (8)
C180.0518 (11)0.0526 (12)0.0612 (11)0.0003 (9)0.0005 (9)0.0094 (9)
C190.0480 (11)0.0617 (13)0.0540 (11)0.0108 (10)0.0012 (9)0.0122 (10)
C200.0407 (10)0.0663 (13)0.0488 (10)0.0059 (9)0.0097 (8)0.0004 (9)
C210.0391 (9)0.0491 (10)0.0449 (9)0.0044 (8)0.0052 (8)0.0084 (8)
Geometric parameters (Å, º) top
O1—C121.362 (2)C8—C91.471 (2)
O1—H1B0.8200C9—C101.371 (3)
O2—C211.367 (2)C9—C141.380 (3)
O2—H2B0.8200C10—C111.379 (3)
N1—N21.3549 (19)C10—H10A0.9300
N1—C81.360 (2)C11—C121.366 (3)
N1—C61.428 (2)C11—H11A0.9300
N2—C151.330 (2)C12—C131.370 (3)
C1—C61.363 (3)C13—C141.376 (3)
C1—C21.374 (3)C13—H13A0.9300
C1—H1A0.9300C14—H14A0.9300
C2—C31.364 (4)C15—C161.455 (2)
C2—H2A0.9300C16—C171.385 (3)
C3—C41.369 (3)C16—C211.394 (2)
C3—H3A0.9300C17—C181.371 (3)
C4—C51.379 (3)C17—H17A0.9300
C4—H4A0.9300C18—C191.377 (3)
C5—C61.371 (3)C18—H18A0.9300
C5—H5A0.9300C19—C201.358 (3)
C7—C81.360 (3)C19—H19A0.9300
C7—C151.401 (2)C20—C211.380 (3)
C7—H7A0.9300C20—H20A0.9300
C12—O1—H1B109.5C11—C10—H10A119.3
C21—O2—H2B109.5C12—C11—C10119.82 (17)
N2—N1—C8111.18 (15)C12—C11—H11A120.1
N2—N1—C6119.34 (14)C10—C11—H11A120.1
C8—N1—C6128.64 (14)O1—C12—C11123.06 (17)
C15—N2—N1105.81 (13)O1—C12—C13117.22 (17)
C6—C1—C2119.5 (2)C11—C12—C13119.71 (16)
C6—C1—H1A120.3C12—C13—C14120.10 (18)
C2—C1—H1A120.3C12—C13—H13A120.0
C3—C2—C1120.0 (2)C14—C13—H13A120.0
C3—C2—H2A120.0C13—C14—C9120.92 (17)
C1—C2—H2A120.0C13—C14—H14A119.5
C2—C3—C4120.4 (2)C9—C14—H14A119.5
C2—C3—H3A119.8N2—C15—C7110.14 (15)
C4—C3—H3A119.8N2—C15—C16119.87 (15)
C3—C4—C5120.0 (2)C7—C15—C16129.96 (16)
C3—C4—H4A120.0C17—C16—C21117.38 (16)
C5—C4—H4A120.0C17—C16—C15120.54 (15)
C6—C5—C4118.9 (2)C21—C16—C15122.04 (16)
C6—C5—H5A120.5C18—C17—C16121.86 (18)
C4—C5—H5A120.5C18—C17—H17A119.1
C1—C6—C5121.20 (19)C16—C17—H17A119.1
C1—C6—N1119.94 (18)C17—C18—C19119.33 (19)
C5—C6—N1118.86 (18)C17—C18—H18A120.3
C8—C7—C15106.22 (15)C19—C18—H18A120.3
C8—C7—H7A126.9C20—C19—C18120.44 (18)
C15—C7—H7A126.9C20—C19—H19A119.8
N1—C8—C7106.65 (14)C18—C19—H19A119.8
N1—C8—C9122.37 (17)C19—C20—C21120.24 (18)
C7—C8—C9130.90 (17)C19—C20—H20A119.9
C10—C9—C14117.98 (16)C21—C20—H20A119.9
C10—C9—C8120.49 (17)O2—C21—C20117.24 (16)
C14—C9—C8121.51 (16)O2—C21—C16122.02 (16)
C9—C10—C11121.40 (18)C20—C21—C16120.73 (18)
C9—C10—H10A119.3
C8—N1—N2—C150.7 (2)C10—C11—C12—O1178.41 (18)
C6—N1—N2—C15171.10 (16)C10—C11—C12—C132.6 (3)
C6—C1—C2—C30.4 (4)O1—C12—C13—C14178.78 (17)
C1—C2—C3—C41.2 (4)C11—C12—C13—C142.2 (3)
C2—C3—C4—C50.9 (3)C12—C13—C14—C90.2 (3)
C3—C4—C5—C60.1 (3)C10—C9—C14—C132.0 (3)
C2—C1—C6—C50.7 (3)C8—C9—C14—C13179.23 (17)
C2—C1—C6—N1179.36 (19)N1—N2—C15—C70.6 (2)
C4—C5—C6—C10.9 (3)N1—N2—C15—C16177.64 (15)
C4—C5—C6—N1179.09 (17)C8—C7—C15—N20.4 (2)
N2—N1—C6—C176.2 (2)C8—C7—C15—C16177.66 (17)
C8—N1—C6—C1115.2 (2)N2—C15—C16—C17175.03 (17)
N2—N1—C6—C5103.7 (2)C7—C15—C16—C177.1 (3)
C8—N1—C6—C564.8 (3)N2—C15—C16—C217.4 (3)
N2—N1—C8—C70.4 (2)C7—C15—C16—C21170.51 (18)
C6—N1—C8—C7169.74 (17)C21—C16—C17—C180.1 (3)
N2—N1—C8—C9177.64 (16)C15—C16—C17—C18177.79 (17)
C6—N1—C8—C913.1 (3)C16—C17—C18—C191.1 (3)
C15—C7—C8—N10.0 (2)C17—C18—C19—C201.1 (3)
C15—C7—C8—C9176.91 (18)C18—C19—C20—C210.1 (3)
N1—C8—C9—C10138.9 (2)C19—C20—C21—O2177.28 (18)
C7—C8—C9—C1044.6 (3)C19—C20—C21—C161.4 (3)
N1—C8—C9—C1442.4 (3)C17—C16—C21—O2177.27 (17)
C7—C8—C9—C14134.1 (2)C15—C16—C21—O20.4 (3)
C14—C9—C10—C111.6 (3)C17—C16—C21—C201.4 (3)
C8—C9—C10—C11179.66 (18)C15—C16—C21—C20179.04 (17)
C9—C10—C11—C120.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O2i0.822.052.824 (2)158
O2—H2B···N20.821.872.595 (2)147
Symmetry code: (i) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC21H16N2O2
Mr328.36
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)10.793 (3), 12.948 (3), 11.705 (3)
β (°) 93.508 (14)
V3)1632.7 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.44 × 0.40 × 0.26
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5767, 3720, 2353
Rint0.024
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.128, 1.03
No. of reflections3720
No. of parameters227
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.16

Computer programs: XSCANS (Siemens, 1999), SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O2i0.8202.0472.824 (2)157.87
O2—H2B···N20.8201.8702.595 (2)146.72
Symmetry code: (i) x1, y+1/2, z1/2.
 

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