2-(2,4-Dichloro­phen­yl)-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)acetamide

Ray J Butcher; Aneeka Mahan; P S Nayak; B Narayana; H S Yathirajan

doi:10.1107/S1600536812049628

. 2012 Dec 8;69(Pt 1):o39. doi: 10.1107/S1600536812049628

2-(2,4-Dichlorophenyl)-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)acetamide

Ray J Butcher ^a,^*, Aneeka Mahan ^b, P S Nayak ^c, B Narayana ^c, H S Yathirajan ^d

PMCID: PMC3588232 PMID: 23476425

Abstract

In the crystal structure of the title compound, C₁₉H₁₇Cl₂N₃O₂, the molecules form dimers of the R ₂ ²(10) type through N—H⋯O hydrogen bonding. As a result of steric repulsion, the amide group is rotated with respect to both the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings, making dihedral angles of 80.70 (13) and 64.82 (12)°, respectively. The dihedral angle between the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings is 48.45 (5)° while that between the 2,3-dihydro-1H-pyrazol-4-yl and phenyl rings is 56.33 (6)°.

Related literature

For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For N-substituted 2-arylacetamides and amides, see: Mijin & Marinkovic (2006 ▶); Mijin et al. (2008 ▶); Fun et al. (2011a ▶,b ▶); Fun, Shahani et al. (2012 ▶); Fun, Quah et al. (2012 ▶); Wu et al. (2008 ▶, 2010 ▶).

Experimental

Crystal data

C₁₉H₁₇Cl₂N₃O₂
M _r = 390.26
Monoclinic,
a = 25.1853 (5) Å
b = 8.18108 (9) Å
c = 21.0978 (4) Å
β = 119.772 (3)°
V = 3773.26 (16) Å³
Z = 8
Cu Kα radiation
μ = 3.25 mm⁻¹
T = 123 K
0.59 × 0.22 × 0.08 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2011 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T _min = 0.429, T _max = 0.804
12628 measured reflections
3849 independent reflections
3663 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.095
S = 1.05
3849 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(20.6KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812049628/bt6879sup1.cif

e-69-00o39-sup1.cif^{(20.6KB, cif)}

Click here for additional data file.^{(188.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049628/bt6879Isup2.hkl

e-69-00o39-Isup2.hkl^{(188.8KB, hkl)}

Click here for additional data file.^{(6.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812049628/bt6879Isup3.cml

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
N1—H1A⋯O2ⁱ	0.88	1.92	2.7938 (15)	171

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Symmetry code: (i) Inline graphic .

Acknowledgments

RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer.

supplementary crystallographic information

Comment

N-Substituted 2-arylacetamides are very interesting compounds because of their structural similarity to the lateral chain of natural benzylpenicillin (Mijin et al., 2006, 2008). Amides are also used as ligands due to their excellent coordination abilities (Wu et al., 2008, 2010). Crystal structures of some acetamide derivatives viz., (2E)-1-(2,5-dimethoxyphenyl)-3-(3-nitrophenyl)prop-2-en-1-one, N-(4-bromophenyl)-2-(naphthalen-1-yl)acetamide, N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-\[4-(methylsulfanyl)phenyl]acetamide, N-(4-bromophenyl)-2-(4-chlorophenyl)acetamide (Fun et al., 2011a; Fun et al., 2011b; Fun, Shahani et al., 2012; Fun, Quah et al., 2012) have been reported. In view of the importance of amides we report herein the crystal structure of the title compound (I).

In the title compound, I, C₁₉H₁₇Cl₂N₃O₂ the amide group is planar and through N—H···O hydrogen bonding to an adjoining molecule forms dimers of the R₂²(10) type (Bernstein et al., 1995). Due to steric repulsion the amide group is rotated with respect to both the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings with dihedral angles of 80.70 (13)° and 64.82 (12)° respectively. The dihedral angles between the three rings are 48.45 (5)° for the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings and and 56.33 (6)° for the 2,3-dihydro-1H-pyrazol-4-yl and phenyl rings, respectively. All other metrical parameters are in the normal ranges (Allen, 2002).

Experimental

2,4-Dichlorophenylacetic acid (0.240 g, 1 mmol) and 4-aminoantipyrine (0.203 g, 1 mmol), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (1.0 g, 0.01 mol) and were dissolved in dichloromethane (20 ml). The mixture was stirred in presence of triethylamine at 273 K for about 3 h. The contents were poured into 100 ml of ice-cold aqueous hydrochloric acid with stirring, which was extracted thrice with dichloromethane. Organic layer was washed with saturated NaHCO₃ solution and brine solution, dried and concentrated under reduced pressure to give the title compound (I). Single crystals were grown from methylene chloride by the slow evaporation method (m.p.: 473–475 K).