[3-(4-Chloro­phen­yl)-5-hydr­oxy-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl](3-pyrid­yl)methanone

Hoong-Kun Fun; Samuel Robinson Jebas; Jyothi N Rao; B Kalluraya

doi:10.1107/S1600536808037161

. 2008 Nov 13;64(Pt 12):o2363–o2364. doi: 10.1107/S1600536808037161

[3-(4-Chlorophenyl)-5-hydroxy-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl](3-pyridyl)methanone

Hoong-Kun Fun ^a,^*, Samuel Robinson Jebas ^a,^‡, Jyothi N Rao ^b, B Kalluraya ^b

PMCID: PMC2959893 PMID: 21581336

Abstract

In the title compound, C₂₁H₁₆ClN₃O₂, the dihedral angles formed by the pyrazole ring with the pyridyl, phenylene and phenyl rings are 6.80 (5), 9.23 (5) and 74.96 (5)°, respectively. The phenyl and phenylene rings are inclined at 80.14 (2)°. Intramolecular O—H⋯O and C—H⋯N hydrogen bonds generate S(6) ring motifs. The crystal packing is strengthened by short intermolecular O—H⋯N, C—H⋯O hydrogen bonds and π–π stacking interactions with centroid–centroid distances of 3.6247 (5)–3.7205 (5) Å, together with intermolecular short O⋯N contacts [2.7682 (11) Å]. Molecules are linked into infinite chains along [100].

Related literature

For the biological applications of pyrazoles, see: Kalluraya & Ramesh (2001 ▶); Watanabe et al. (1998 ▶); Yuhong & Rajender (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₁H₁₆ClN₃O₂
M _r = 377.82
Triclinic,
a = 7.5916 (1) Å
b = 9.7644 (1) Å
c = 12.5474 (2) Å
α = 104.424 (1)°
β = 94.960 (1)°
γ = 96.081 (1)°
V = 889.55 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100.0 (1) K
0.47 × 0.29 × 0.19 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.896, T _max = 0.957
20326 measured reflections
6385 independent reflections
5630 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.103
S = 1.04
6385 reflections
248 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037161/ng2515sup1.cif

e-64-o2363-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037161/ng2515Isup2.hkl

e-64-o2363-Isup2.hkl^{(306.2KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O1	0.824 (13)	2.340 (14)	2.8463 (9)	120.3 (13)
O2—H1O2⋯N3ⁱ	0.824 (13)	2.027 (14)	2.7682 (11)	149.5 (14)
C8—H8A⋯O2ⁱⁱ	0.97	2.55	3.4836 (11)	163
C13—H13A⋯O1ⁱⁱⁱ	0.93	2.46	3.3294 (12)	156
C21—H21A⋯N1	0.93	2.21	2.8600 (12)	127
C14—H14A⋯Cg2^iv	0.93	2.90	3.6968 (11)	144

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the N3/C17–C21 ring.

Acknowledgments

FHK and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a postdoctoral research fellowship.

supplementary crystallographic information

Comment

Heterocyclic compounds occur very widely in nature and are essential to life. Nitrogen-containing heterocyclic molecules constitute the largest portion of chemical entities, which are part of many natural products, fine chemicals, and biologically active pharmaceuticals vital for enhancing the quality of life. 4,5-Dihydro-pyrazoles, pyrazolidines and 1,2-dihydro-phthalazines are important classes of heterocycles useful as pesticides, anticonvulsants, and potent vasorelaxing agents (Kalluraya et al., 2001; Watanabe et al., 1998; Yuhong & Rajender, 2005). The pyrazoline function is quite stable and has inspired chemists to utilize this stable fragment in bioactive moieties to synthesize new compounds. Prompted by these review, we have synthesized this new substituted pyrazoline derivative and report its crystal structure.

Bond lengths and angles in (I) (Fig. 1) are found to have normal values (Allen et al., 1987). The dihedral angle formed by the pyrazole (N1/N2/C7—C9) ring with the pyridine ring (N3/C17—C21) and the two benzene rings (C1—C6; C10—C15) are 6.80 (5), 9.23 (5) and 74.96 (5)° respectively. The benzene rings (C1—C6; C10—C15) form dihedral angle of 80.14 (2)°, indicating that they are inclined to each other. Intramolecular C—H···N and O—H···O hydrogen bonds generate S(6) ring motifs. (Bernstein et al., 1995).

The crystal packing is consolidated by intermolecular O—H···N and C—H···O hydrogen bonding (Table 1). Furthermore, the packing is strengthened by π—π stacking interactions involving the pyrazole (N1—N2/C7—C9) (Cg1) ring and the symmetry related benzene (C10—C15) (Cg4) ring [Cg1···Cg4^v=3.7787 (6) Å; symmetry code: (v) X,Y,Z]; pyridine (N3/C17—C21) (Cg2) ring and the symmetry related benzene (C1—C6) (Cg3) ring [Cg2···Cg3^vi=3.6247 (5) Å; symmetry code: (vi) –X,-Y,2-Z] and between symmetry related benzene (C1—C6) (Cg3) rings [Cg3···Cg3^vii = 3.7205 (5) Å; symmetry code: (vii) –X,1-Y,2-Z] together with intermolecular O···N = 2.7682 (11)Å short contacts. In the crystal packing, the molecules are linked into infinite one dimensional chains along the [100] direction (Fig 2).

Experimental

A mixture of 1-phenyl-3-(4-chloro phenyl)-2,3-di-bromo propan-1-one (0.01 mol), nicotinic hydrazide (0.01 mol) and trimethylamine (0.04 mol) in ethanol (30 mL) was refluxed for 8 h. The contents were poured onto crushed ice with stirring. The solid mass separated was collected and recrystallized from ethanol.