Crystal structure of 4-[(2,4-di­chloro­phen­yl)(5-hy­droxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)meth­yl]-5-methyl-2-phenyl-2,3-di­hydro-1H-pyrazol-3-one

Balbir Kumar; Hitesh Mahajan; Satya Paul; Rajni Kant; Vivek K Gupta

doi:10.1107/S2056989015017880

. 2015 Sep 30;71(Pt 10):o805–o806. doi: 10.1107/S2056989015017880

Crystal structure of 4-[(2,4-dichlorophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl]-5-methyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one

Balbir Kumar ^a, Hitesh Mahajan ^b, Satya Paul ^b, Rajni Kant ^a, Vivek K Gupta ^a,^*

PMCID: PMC4647350 PMID: 26594489

Abstract

In the title compound C₂₇H₂₂Cl₂N₄O₂, the pyrazol-5-ol ring makes a dihedral angle of 34.80 (11)° with the phenyl ring to which it is bound, while the pyrazolone ring is inclined at 34.34 (12)° to its attached phenyl ring. In the crystal, N—H⋯O and C—H⋯Cl hydrogen bonds link the molecules into chains along [010]. Intermolecular π–π interactions are observed between the pyrazolone ring and the phenyl ring bound to the pyrazol-5-ol ring system [centroid–centroid separation = 3.916 (2) Å].

Keywords: crystal structure, pyrazolone, hydrogen bonding, π–π interactions

Related literature

For the biological activity of bis-pyrazolones, see: Park et al. (2005 ▸), and for their applications see: Bailey et al. (1985 ▸); Rosiere & Grossman (1951 ▸); Mahajan et al. (1991 ▸); Chauhan et al. (1993 ▸); Hamama et al. (2001 ▸). For the synthesis of similar compounds, see: Bhardwaj et al. (2015 ▸); Niknam & Mirzaee (2011 ▸). For related structures, see: Sharma et al. (2014 ▸).

Experimental

Crystal data

C₂₇H₂₂Cl₂N₄O₂
M _r = 505.39
Monoclinic
a = 19.8321 (19) Å
b = 7.8574 (5) Å
c = 16.3416 (16) Å
β = 106.815 (10)°
V = 2437.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Agilent Xcalibur, Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▸) T _min = 0.751, T _max = 1.000
9479 measured reflections
4775 independent reflections
2524 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.174
S = 1.00
4775 reflections
318 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015017880/sj5478sup1.cif

e-71-0o805-sup1.cif^{(30.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017880/sj5478Isup2.hkl

e-71-0o805-Isup2.hkl^{(229.2KB, hkl)}

Click here for additional data file.^{(9.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015017880/sj5478Isup3.cml

Click here for additional data file.^{(1.7MB, tif)}

ORTEP . DOI: 10.1107/S2056989015017880/sj5478fig1.tif

ORTEP view of the molecule with the atom-labeling scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.

Click here for additional data file.^{(3.2MB, tif)}

a . DOI: 10.1107/S2056989015017880/sj5478fig2.tif

The packing arrangement of molecules viewed along the a axis.

CCDC reference: 1427164

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H2O27ⁱ	0.86	2.08	2.756(3)	135
C24H24ACl1ⁱⁱ	0.96	2.93	3.823(3)	156

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003.

supplementary crystallographic information

S1. Comment

Bis-pyrazolones are an important class of heterocyclic compounds which have risen to prominence in recent years due to their vital role in various biological activities such as selective COX-2 inhibition, antitumor and cytokine inhibition (Park et al., 2005). Bis-pyrazolones are also used as antidepressants (Bailey et al., 1985), gastric secretion stimulators (Rosiere & Grossman, 1951), or as antibacterial (Mahajan et al., 1991) and antifilarial agents (Chauhan et al., 1993). Moreover, 4,4'-(arylmethylene) bis(1H-pyrazol-5-ols) are used as pesticides, fungicides and dye stuffs (Hamama et al., 2001). In recent years, different reagents have been reported for the synthesis of 4,4'-(arylmethylene)bis(3-methyl-1-phenyl-pyrazol-5-ol) derivatives including the condensation reaction between arylaldehyde and 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (Niknam & Mirzaee, 2011; Bhardwaj et al., 2015).

In the title compound C₂₇H₂₂C₁₂N₄O₂, the pyrazole rings N1/N2/C3/C4/C5 and N6/N7/C8/C9/C10 make dihedral angle of 34.80 (11)° and 34.34 (12)° with the phenyl rings C18/C19/C20/C21/C22/C23 and C28/C29/C30/C31/C32/C33 respectively. The C5═O26 double bond [1.277 (3) Å] is significantly longer than that normally observed for carbonyl bonds [1.19 Å], probably because the hydroxyl group and carbonyl oxygen atom are involved in an intermolecular O—H···O hydrogen bond and is comparable with that found in a related structure (Sharma et al., (2014). The bond lengths of C15—Cl1 [1.729 (4) Å] and C13—Cl2 [1.730 (4) Å], are comparable with the accepted value of 1.739 Å and are in good agreement with another molecule of this type (Sharma et al., 2014). π - π interactions are observed between the pyrazole ring (N1/N2/C3/C4/C5) and phenyl ring (C28/C29/C30/C31/C32/C33) [centroid–centroidⁱ seperation = 3.916 (2) Å, interplanar spacing = 3.784 Å, centroid shift = 1.01 Å for symmetry operation: x, 1 + y, z]. Classical N–H···O and non-classical C–H···Cl hydrogen bonds, Table 1, also stabilise the crystal packing.

S2. Experimental

Synthesis of 4-[(2,4-dichlorophenyl)(5-hydroxy-3-methyl-1-phenyl- 1H-pyrazol-4-yl)methyl]-1,2-dihydro-5-methyl-2-phenyl- 3H-pyrazol-3-one: To a mixture of 2,4-dichlorobenzaldehyde (1 mmol) and 5-methyl-2-phenyl-2, 4-dihydro-3H-pyrazol-3-one (2 mmol), melt of imidazole-DMU (30:70) was added and the reaction mixture was stirred at 70 ° C for the appropriate time. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature and diluted with water (20 ml). The product was extracted with EtOAc (20 ml) and dried over anhydrous Na₂SO₄. Removal of the solvent under reduced pressure gave 4-[(2,4-dichlorophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl) methyl]-1,2-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one which was purified by crystallization from ethyl acetate:pet ether. The product, was obtained as shiny white crystals.